CN106186049A - A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable - Google Patents
A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable Download PDFInfo
- Publication number
- CN106186049A CN106186049A CN201610557526.9A CN201610557526A CN106186049A CN 106186049 A CN106186049 A CN 106186049A CN 201610557526 A CN201610557526 A CN 201610557526A CN 106186049 A CN106186049 A CN 106186049A
- Authority
- CN
- China
- Prior art keywords
- germanate
- bar
- sodium
- zinc
- shaped zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 56
- 239000011701 zinc Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 18
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004246 zinc acetate Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 235000001014 amino acid Nutrition 0.000 claims abstract description 12
- 150000001413 amino acids Chemical class 0.000 claims abstract description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 235000013904 zinc acetate Nutrition 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 239000004475 Arginine Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 4
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 4
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims 1
- 239000004472 Lysine Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000014304 histidine Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000696 methanogenic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses the hydrothermal preparing process of the bar-shaped zinc germanate of a kind of size adjustable, comprise the steps: prepared by (1) presoma: mix with the ratio that mol ratio is 1:1 of germanium oxide pressed powder in sodium carbonate, under the conditions of temperature is 700～1000 DEG C, calcines 8～24h, prepares sodium germanate pressed powder；(2) with sodium germanate as ge source, being added by aminoacid in sodium germanate solution, its sodium germanate and the amino acid whose mol ratio that adds are 1:0.5～5；Stir under the conditions of mixed solution is placed in 40～80 DEG C；(3) zinc acetate solution adding the mixed solution in step (2), wherein zinc acetate is 1:1 with the mol ratio that adds of sodium germanate；Mixed solution is loaded in reactor, in temperature be 120～200 DEG C of Water Under thermal response times be 3～12h, product is washed to neutrality, and drying under reduced pressure grinds and prepares bar-shaped zinc germanate.The present invention is easy and simple to handle, sodium germanate nanometer rods size adjustable, can synthesize in a large number, with low cost.
Description
Technical field
The invention belongs to materials synthesis field, be specifically related to the hydro-thermal preparation side of the bar-shaped zinc germanate of a kind of size adjustable
Method.
Background technology
Zinc germanate is the compound of the p district metal ion containing d10 electronic structure, and atom is distributed along c-axis, each germanium atom
It is positioned in the tetrahedron being made up of 4 oxygen atoms with zinc atom.Its special structures shape zinc germanate has good thermally-stabilised
Property, high brightness and the plurality of advantages such as be easily worked, thus become the ideal material of electroluminescent and Field Emission Display.Germanium
Acid zinc not only possesses good luminescent properties, or excellent photocatalyst, mainly for the treatment of persistent organic pollutants, divides
Xie Shui and reduction carbon dioxide.The microstructure of zinc germanate material, particularly pattern and size etc. are to its performance, stability and answer
Apparatus has significant effect.
Synthesize bar-shaped zinc germanate at present it is generally required to add ethylenediamine, sodium cetanesulfonate, polyvinylpyrrolidone etc.
Surfactant.Building-up process is complicated, relatively costly, productivity is relatively low and product morphology is single, limits the work of bar-shaped zinc germanate
Industry is applied.
At present, lack a kind of controllable with low cost and synthesize the preparation method of a large amount of various sizes of bar-shaped zinc germanate,
For meeting its specific demand to scantling in the special-purposes such as luminescence, photocatalysis.Aminoacid is utilized to live as surface
Property agent, the bar-shaped zinc germanate of high yield of synthesis size adjustable is not reported so far.
Summary of the invention
The technical problem to be solved is to provide controllable with low cost and synthesizes various sizes of bar-shaped germanic acid
The preparation method of zinc.
To achieve these goals, the present invention is achieved through the following technical solutions: the invention provides a kind of size adjustable
The hydrothermal preparing process of bar-shaped zinc germanate, comprise the steps:
(1) prepared by presoma: mix with germanium oxide pressed powder by sodium carbonate, grinds, mixture is placed in horse under room temperature
Not in stove, being warming up to 700～1000 DEG C in room temperature through 70～100min, after insulation 8～24h, fast decompression cools down, gained germanium
Acid sodium solid grinds further；
(2) with sodium germanate as ge source, it is made into sodium germanate solution, using aminoacid as surfactant, is added into
To sodium germanate solution, stir under the conditions of mixed solution is placed in 40～80 DEG C；
(3) using Zinc diacetate dihydrate as zinc source, it is made into zinc acetate solution, zinc acetate solution is added step (2)
In mixed solution, mixed solution is loaded in reactor, is placed in baking oven, being warming up to temperature in room temperature through 30～100min is
120～200 DEG C, after insulation 3～12h, fast decompression cools down, and products therefrom is through repeatedly washing, until neutral, is put by products therefrom
In baking oven after drying, prepared bar-shaped zinc germanate is ground.
Further, in step (1), the mixture of sodium carbonate and germanium oxide pressed powder first passes through the program of 70～100min
Heat up after room temperature rises to 700～1000 DEG C, be incubated 8～24h, and obtain sodium germanate pressed powder by fast decompression cooling.
Further, in step (1), the mol ratio of sodium carbonate and germanium oxide pressed powder is 1:1.
Further, in step (2), sodium germanate solution concentration is 0.01～0.05mol/L, sodium germanate and amino acid whose mole
Ratio is 1:0.5～5.
Further, in step (2), involved aminoacid includes tryptophan, glycine, serine, tyrosine, relies ammonia
One in acid, arginine, histidine, aspartic acid, glutamic acid.Wherein the zinc germanate nanometer rods synthesized by arginine is urged at light
Change in the reduction methanogenic application of carbon dioxide and be demonstrated by good photocatalysis performance.
Further, in step (3), zinc acetate solution concentration is 0.01～0.1mol/L, zinc acetate and the mol ratio of sodium germanate
For 1:1.
The size of bar-shaped zinc germanate prepared by the present invention is 50nm～5 μm.
The present invention is by adding the crystal anisotropic growth speed of the aminoacid scalable zinc germanate containing different functional groups
Rate, thus synthesize various sizes of bar-shaped zinc germanate.The method can meet zinc germanate in different purposes (such as luminous, photocatalysis
Deng) on specific demand to scantling.
Beneficial effect:
The present invention utilizes different aminoacid as surfactant, its role is to by the ammonia containing different functional groups
Crystalline anisotropy's growth rate of base acid regulation and control zinc germanate, has reached to synthesize size adjustable, the bar-shaped zinc germanate of high yield；Should
Method can meet the zinc germanate specific demand to scantling on different purposes (such as luminescence, photocatalysis etc.).Institute of the present invention
The technological operation synthesizing bar-shaped zinc germanate related to is easy, can synthesize in a large number, with low cost, mild condition, and technique is simple, has
The prospect of large-scale production；Product has higher specific surface area, it is expected to be applied as luminescent material and catalysis material.
Accompanying drawing explanation
Fig. 1 be the present invention relates to by the bar-shaped zinc germanate prepared by specific embodiment 1 SEM scheme；
Fig. 2 be the present invention relates to by the bar-shaped zinc germanate prepared by specific embodiment 2 SEM scheme；
Fig. 3 be the present invention relates to by the bar-shaped zinc germanate prepared by specific embodiment 3 SEM scheme；
Fig. 4 be the present invention relates to by the bar-shaped zinc germanate prepared by specific embodiment 4 SEM scheme.
Fig. 5 be the present invention relates to by the XRD figure of bar-shaped zinc germanate synthesized by specific embodiment 1～4.
Detailed description of the invention
By combining the drawings and specific embodiments, the present invention further will be specifically described below, but it is not intended that
It it is limiting the scope of the present invention.
Embodiment 1
The invention provides the hydrothermal preparing process of the bar-shaped zinc germanate of a kind of size adjustable, comprise the steps:
(1) prepared by presoma: mix, under room temperature with the ratio that mol ratio is 1:1 of germanium oxide pressed powder in sodium carbonate
Grinding 30, be placed in Muffle furnace by mixture, be warming up to 700 DEG C in room temperature through 70, after insulation 8h, fast decompression cools down, institute
Obtain sodium germanate solid and grind 60min further；
(2) with sodium germanate as ge source, it is made into the sodium germanate solution that concentration is 0.01mol/L, using arginine as table
Face activating agent, is added into sodium germanate solution, and wherein sodium germanate and arginic mol ratio are 1:0.5；By mixed solution
Stir under the conditions of being placed in 40 DEG C；
(3) using Zinc diacetate dihydrate as zinc source, it is made into the zinc acetate solution that concentration is 0.01mol/L, by acetic acid
Zinc solution adds the mixed solution in step (2), and wherein zinc acetate is 1:1 with the mol ratio of sodium germanate；Mixed solution is loaded
In reactor, being placed in baking oven, being warming up to temperature in room temperature through 30 is 120, and after insulation 3h, fast decompression cools down, products therefrom
Through repeatedly washing, until neutral, products therefrom is placed in baking oven dried, grinds and prepare bar-shaped zinc germanate.
Knowable to Fig. 1 scanning electron microscope (SEM) photograph, the size of the bar-shaped zinc germanate sample prepared by embodiment 1 it is about 70nm,
It is labeled as sample 1.
Knowable to the XRD figure of Fig. 5, the sample prepared by embodiment 1 it is zinc germanate.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1:
(1) prepared by presoma: mix, under room temperature with the ratio that mol ratio is 1:1 of germanium oxide pressed powder in sodium carbonate
Grind 40min, mixture is placed in Muffle furnace, is warming up to 800 DEG C in room temperature through 80min, after insulation 12h, fast decompression
Cooling, gained sodium germanate solid grinds about 40min further；
(2) with sodium germanate as ge source, it is made into the sodium germanate solution that concentration is 0.02mol/L, using tyrosine as table
Face activating agent, is added into sodium germanate solution, and wherein sodium germanate is 1:2 with the mol ratio of tyrosine；Mixed solution is put
Stir under the conditions of 50 DEG C；
(3) using Zinc diacetate dihydrate as zinc source, it is made into the zinc acetate solution that concentration is 0.02mol/L, by acetic acid
Zinc solution adds the mixed solution in step (2), and wherein zinc acetate is 1:1 with the mol ratio of sodium germanate；Mixed solution is loaded
In reactor, being placed in baking oven, being warming up to temperature in room temperature through 50min is 150 DEG C, and after insulation 5h, fast decompression cools down, gained
Product is through repeatedly washing, until neutral, be placed in baking oven by products therefrom dried, grind and prepare bar-shaped zinc germanate.
Knowable to the scanning electron microscope (SEM) photograph of Fig. 2, the size of the bar-shaped zinc germanate prepared by embodiment 2 it is 500nm, is labeled as
Sample 2.
Knowable to the XRD figure of Fig. 5, the sample prepared by embodiment 2 it is zinc germanate.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1:
(1) prepared by presoma: mix, under room temperature with the ratio that mol ratio is 1:1 of germanium oxide pressed powder in sodium carbonate
Grind 50min, mixture is placed in Muffle furnace, is warming up to 900 DEG C in room temperature through 90min, after insulation 16h, fast decompression
Cooling, gained sodium germanate solid grinds about 50min further；
(2) with sodium germanate as ge source, it is made into the sodium germanate solution that concentration is 0.04mol/L, using tryptophan as table
Face activating agent, is added into sodium germanate solution, and wherein sodium germanate is 1:3 with the mol ratio of tryptophan；Mixed solution is put
Stir under the conditions of 60 DEG C；
(3) using Zinc diacetate dihydrate as zinc source, it is made into the zinc acetate solution that concentration is 0.05mol/L, by acetic acid
Zinc solution adds the mixed solution in step (2), and wherein zinc acetate is 1:1 with the mol ratio of sodium germanate；Mixed solution is loaded
In reactor, being placed in baking oven, being warming up to temperature in room temperature through 80min is 180 DEG C, and after insulation 8h, fast decompression cools down, gained
Product is through repeatedly washing, until neutral, be placed in baking oven by products therefrom dried, grind and prepare bar-shaped zinc germanate.
Knowable to the scanning electron microscope (SEM) photograph of Fig. 3, the size of the bar-shaped zinc germanate prepared by embodiment 3 it is 1.5 μm, is labeled as
Sample 3.
Knowable to the XRD figure of Fig. 5, the sample prepared by embodiment 3 it is zinc germanate.
Claims (8)
1. the hydrothermal preparing process of the bar-shaped zinc germanate of a size adjustable, it is characterised in that: comprise the steps:
(1) prepared by presoma: mix with germanium oxide pressed powder by sodium carbonate, grinds, mixture is placed in Muffle furnace under room temperature
In, it being warming up to 700～1000 DEG C in room temperature through 70～100min, after insulation 8～24h, fast decompression cools down, gained sodium germanate
Solid grinds further；
(2) with sodium germanate as ge source, it is made into sodium germanate solution, using aminoacid as surfactant, is added into germanium
In acid sodium solution, stir under the conditions of mixed solution is placed in 40～80 DEG C；
(3) using Zinc diacetate dihydrate as zinc source, it is made into zinc acetate solution, zinc acetate solution is added in step (2)
Mixed solution, loads mixed solution in reactor, is placed in baking oven, and being warming up to temperature in room temperature through 30～100min is 120
～200 DEG C, after insulation 3～12h, fast decompression cools down, and products therefrom is through repeatedly washing, until neutral, is placed in by products therefrom
In baking oven after drying, prepared bar-shaped zinc germanate is ground.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: in step
(1) in, the mixture of sodium carbonate and germanium oxide pressed powder first pass through the temperature programming of 70～100min from room temperature rise to 700～
After 1000 DEG C, it is incubated 8～24h, and obtains sodium germanate pressed powder by fast decompression cooling.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: step
(1) in, sodium carbonate is 1:1 with the mol ratio of germanium oxide pressed powder.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: step
(2) in, sodium germanate solution concentration is 0.01～0.05mol/L, and sodium germanate and amino acid whose mol ratio are 1:0.5～5.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: in step
(2), in, involved aminoacid includes tryptophan, glycine, serine, tyrosine, lysine, arginine, histidine, Radix Asparagi
One in propylhomoserin, glutamic acid.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 5, it is characterised in that: in step
(2), in, involved aminoacid is arginine.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: step
(3) in, zinc acetate solution concentration is 0.01～0.1mol/L, and zinc acetate is 1:1 with the mol ratio of sodium germanate.
The hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable the most according to claim 1, it is characterised in that: preparation
The size of bar-shaped zinc germanate is 50nm～5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610557526.9A CN106186049A (en) | 2016-07-14 | 2016-07-14 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610557526.9A CN106186049A (en) | 2016-07-14 | 2016-07-14 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106186049A true CN106186049A (en) | 2016-12-07 |
Family
ID=57474666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610557526.9A Pending CN106186049A (en) | 2016-07-14 | 2016-07-14 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106186049A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634206A (en) * | 2017-09-15 | 2018-01-26 | 江苏科技大学 | A kind of lithium ion battery flexibility negative material and preparation method thereof |
| CN108622928A (en) * | 2018-04-14 | 2018-10-09 | 滁州博创能源科技有限公司 | A kind of preparation method and application of the germanic acid zinc nano material of morphology controllable |
| CN108793231A (en) * | 2018-08-13 | 2018-11-13 | 江苏理工学院 | The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles |
| CN108956716A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of flexible gas sensor and preparation method thereof based on printable micron linear array sensitive layer |
| CN109292734A (en) * | 2018-09-26 | 2019-02-01 | 吉林大学 | A kind of room temperature flexible gas sensor and preparation method thereof based on polycrystalline micro wire grain boundary effect |
| CN109589985A (en) * | 2018-12-19 | 2019-04-09 | 荣吴迪 | The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate |
| CN110510662A (en) * | 2019-10-11 | 2019-11-29 | 安徽工业大学 | A kind of germanic acid erbium nanorod electrodes material and preparation method thereof |
| CN110556525A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN111285410A (en) * | 2020-02-10 | 2020-06-16 | 广州大学 | Carbon composite metal oxide nanosheet material and preparation method and application thereof |
| CN114538500A (en) * | 2022-03-09 | 2022-05-27 | 郑州轻工业大学 | Bar-shaped structure Zn2GeO4Material, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350307A (en) * | 2011-06-30 | 2012-02-15 | 东华大学 | Preparation method of hybrid nano film |
| CN102962049A (en) * | 2012-11-26 | 2013-03-13 | 南京大学 | Method for preparing nanometer photocatalytic material via hydrothermal reaction |
| CN103449524A (en) * | 2013-08-23 | 2013-12-18 | 东华大学 | Molybdenum oxide based nano photothermal conversion material and preparation method thereof |
| CN104646040A (en) * | 2015-02-15 | 2015-05-27 | 济南大学 | Preparation method and application of BiOI/Zn2GeO4 heterojunction visible-light-induced photocatalyst |
-
2016
- 2016-07-14 CN CN201610557526.9A patent/CN106186049A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350307A (en) * | 2011-06-30 | 2012-02-15 | 东华大学 | Preparation method of hybrid nano film |
| CN102962049A (en) * | 2012-11-26 | 2013-03-13 | 南京大学 | Method for preparing nanometer photocatalytic material via hydrothermal reaction |
| CN103449524A (en) * | 2013-08-23 | 2013-12-18 | 东华大学 | Molybdenum oxide based nano photothermal conversion material and preparation method thereof |
| CN104646040A (en) * | 2015-02-15 | 2015-05-27 | 济南大学 | Preparation method and application of BiOI/Zn2GeO4 heterojunction visible-light-induced photocatalyst |
Non-Patent Citations (4)
| Title |
|---|
| 单连娟: "氨基酸辅助水热法制备稀土氟化物纳米发光材料", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 宋玲玲: "基于碳酸钙和氧化物纳米结构制备与表征", 《氨基酸辅助水热法制备稀土氟化物纳米发光材料》 * |
| 张亚平: "从浸锌渣还原铁粉中回收镓锗的工艺及机理", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 王万坤: "微波焙烧含锗氧化锌烟尘回收锗的研究", 《中国博士学位论文全文数据库信息科技辑》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634206A (en) * | 2017-09-15 | 2018-01-26 | 江苏科技大学 | A kind of lithium ion battery flexibility negative material and preparation method thereof |
| CN107634206B (en) * | 2017-09-15 | 2020-06-05 | 江苏科技大学 | Flexible negative electrode material of lithium ion battery and preparation method thereof |
| CN108622928A (en) * | 2018-04-14 | 2018-10-09 | 滁州博创能源科技有限公司 | A kind of preparation method and application of the germanic acid zinc nano material of morphology controllable |
| CN108956716A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of flexible gas sensor and preparation method thereof based on printable micron linear array sensitive layer |
| CN108793231A (en) * | 2018-08-13 | 2018-11-13 | 江苏理工学院 | The method that molten-salt growth method synthesizes fusiform germanic acid zinc nanoparticles |
| CN109292734A (en) * | 2018-09-26 | 2019-02-01 | 吉林大学 | A kind of room temperature flexible gas sensor and preparation method thereof based on polycrystalline micro wire grain boundary effect |
| CN109589985A (en) * | 2018-12-19 | 2019-04-09 | 荣吴迪 | The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate |
| CN109589985B (en) * | 2018-12-19 | 2020-05-01 | 荣吴迪 | Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate |
| CN110556525A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN110556525B (en) * | 2019-08-21 | 2022-03-29 | 华南理工大学 | Lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN110510662A (en) * | 2019-10-11 | 2019-11-29 | 安徽工业大学 | A kind of germanic acid erbium nanorod electrodes material and preparation method thereof |
| CN111285410A (en) * | 2020-02-10 | 2020-06-16 | 广州大学 | Carbon composite metal oxide nanosheet material and preparation method and application thereof |
| CN111285410B (en) * | 2020-02-10 | 2022-07-05 | 广州大学 | Carbon composite metal oxide nanosheet material and preparation method and application thereof |
| CN114538500A (en) * | 2022-03-09 | 2022-05-27 | 郑州轻工业大学 | Bar-shaped structure Zn2GeO4Material, preparation method and application thereof |
| CN114538500B (en) * | 2022-03-09 | 2023-11-03 | 郑州轻工业大学 | Rod-shaped structure Zn 2 GeO 4 Material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106186049A (en) | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable | |
| CN104973615B (en) | Microwave burning preparation method of nano gadolinium oxide powder | |
| CN106938854A (en) | A kind of preparation method of large scale lead halide caesium perovskite crystal | |
| CN106622331A (en) | Preparation method of high-specific-surface-area graphite phase carbon nitride photocatalyst | |
| CN108314077A (en) | The simple method for preparing full-inorganic perovskite nanostructure | |
| Chou et al. | The optimum conditions for solid-state-prepared (Y3− xCex) Al5O12 phosphor using the Taguchi method | |
| CN111151282B (en) | Nitrogen-doped graphite-like phase carbon nitride visible-light-induced photocatalyst and preparation method and application thereof | |
| CN102071017B (en) | Preparation method of aluminate blue fluorescent powder for three-color light-emitting diode | |
| CN104477977B (en) | The synthetic Dy of a kind of molten-salt growth method2TiO5The method of powder | |
| CN109775750B (en) | Solution method for preparing all-inorganic perovskite CsPbBr3Method for preparing nanowires and up-conversion luminescent material | |
| CN106311306B (en) | A method of preparing lithium doping graphite phase carbon nitride material | |
| CN108031483A (en) | A kind of TiO of carbon coating N doping2Butterfly-like nano material synthetic method | |
| CN104387081A (en) | Low-temperature preparation method of transparent aluminum oxynitride (AlON) ceramic | |
| CN104893723A (en) | Method for preparing YAG-Ce phosphor by using combustion method | |
| CN103466688B (en) | A kind of method for preparing ZnS nanosheet | |
| CN104692387A (en) | Method for preparing nanometer silicon carbide by using silicon-containing biomass as raw material at low temperature and prepared nanometer silicon carbide | |
| CN115851273B (en) | Rare earth doped perovskite nanocrystalline synthesis method | |
| CN108048091A (en) | It is a kind of to prepare NaYF using thermal decomposition method4The method of core-shell nano crystalline substance | |
| CN104528814A (en) | Preparation method and product of CaTi2O4(OH)4 diamond nanosheet with lamellar structure | |
| CN109761207B (en) | 3D graphite phase carbon nitride material and preparation method thereof | |
| CN104071844A (en) | Burning method for preparing Sr2YTaO6 powder | |
| CN110817927A (en) | Method for preparing light porous nano cerium oxide by combustion method | |
| CN104760940A (en) | A synthetic method of sandwich type composite carbon nitride | |
| CN105110376B (en) | A kind of quick method preparing olive-shaped wolframic acid lanthanum sodium | |
| CN108585040B (en) | CeVO4Quick preparation method of functional material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161207 |