CN104692349B - Method for performing CO2-enriched hydrothermal synthesis to gadolinium phosphate nanorod - Google Patents
Method for performing CO2-enriched hydrothermal synthesis to gadolinium phosphate nanorod Download PDFInfo
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- CN104692349B CN104692349B CN201410810264.3A CN201410810264A CN104692349B CN 104692349 B CN104692349 B CN 104692349B CN 201410810264 A CN201410810264 A CN 201410810264A CN 104692349 B CN104692349 B CN 104692349B
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- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 10
- 239000002073 nanorod Substances 0.000 title abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 230000002085 persistent effect Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 10
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000005696 Diammonium phosphate Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- -1 rare earth phosphate Chemical class 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical group [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a method for performing CO2-enriched hydrothermal synthesis to a gadolinium phosphate nanorod. The method is characterized by comprising the following steps: respectively preparing a Gd＜3+＞ salt solution and a PO4＜3+＞ solution at room temperature; adding the two solutions into the reaction kettle according to the volume ratio of 1:1, stirring while adding, continuously stirring for 30min to 1h; introducing CO2 gas or dry ice into the reaction kettle, controlling the pressure in the kettle to be 1-10Mpa, and sealing and heating the high-pressure reaction kettle, setting the reaction temperature to be 100-200DEG C and the lasting time to be 12h-2d, then naturally cooling the high-pressure reaction kettle to room temperature; filtering the reacted product, washing sequentially with deionized water and anhydrous ethanol and centrifuging for twice; and drying the dried and centrifuged product for more than 6h at 50-100DEG C, thus obtaining a final pure product.
Description
Technical field
The present invention relates to the preparation method of a kind of rare earth phosphate nanometer material, belong to functional material synthesis technical field.
Background technology
In the periodic table of elements, gadolinium (Gd) is positioned at IIIB race, and atomic number is 64, belongs to LREE, and gadolinium content in the earth's crust is 0.000636%.In addition, the element of atomic number 57 to 71, they and gadolinium are collectively known as lanthanide series.Lanthanide series is referred to as rare earth element with yttrium (Y) of the same clan and scandium (Sc).Rare earth element has special electron structure (4f0-145d0-16s2), their outer-shell electron is essentially identical, internal layer 4f electron energy level is the most close, and 4f is the shell of a underfill, electron orbit is the most empty, half ion being full of and being entirely full of electronics has optics inertia, for stable state, because of the feature of its outer electronic structure so that it is have special physicochemical properties.
RE phosphate material, because having the advantages such as coefficient of refraction that in good heat stability, water, dissolubility is minimum and high, is widely used in the fields such as luminescent material, ceramic material, catalyst, alloy material and lubriation material.Gadolinium monophosphate (GdPO4), the good substrate of other rare earth ion that is often used as adulterating.Luminescent material with nanometer Gadolinium monophosphate as substrate has good stability, thermal capacitance is big, have high efficiency feature under the exciting of vacuum-ultraviolet light, simultaneously because material particle size is less than exciting or launching optical wavelength, therefore light field can be approximately uniform in particle range, can significantly improve cathode ray tube and plasma display definition.Meanwhile, Gadolinium monophosphate fusing point is high, is combined with some oxides, such as Al2O3, the composite ceramics processed high temperature resistant, that antioxidation, electrical insulating property are good can be prepared.It addition, Gadolinium monophosphate is also widely used for alloy material, catalysis material.Therefore the Gadolinium monophosphate studying controlled monazite structure has great importance.
Synthesizing rare-earth phosphate mainly has the methods such as sol-gal process, hydro-thermal method, the sedimentation method, solid phase method, combustion method and microwave method at present, wherein commonplace with hydrothermal synthesis method.Existing numerous studies show that pH is to control one of rare earth phosphate nanometer material crystal form most important factor of crystalline substance looks, but the method using Syntheses in water RE phosphate at present, all simply in initial aqueous solution, have adjusted pH, there is no buffer pH, lacked the control to its crystal form crystalline substance looks of the gradual change physical and chemical condition, exist crystallization degree be not the highest, size be not very uniformly, problem that controllability is the strongest.In nature, the geologic fluids that the Ree-phospeate Minerals of hydrothermal origin is formed is generally of certain CO2Dividing potential drop, CO in hydrothermal solution2Can be with the pH of buffer solution.The present invention is by making full use of CO2The feature of dividing potential drop buffer solution pH, Hydrothermal Synthesis purity height, size uniform, crystallization degree is good, controllability is strong Gadolinium monophosphate nanometer rods.
Summary of the invention
The technical problem to be solved in the present invention is: provide one to make full use of CO2The feature of dividing potential drop buffer solution pH, Hydrothermal Synthesis purity height, size uniform, the method for crystallization degree is good, controllability is strong Gadolinium monophosphate nanometer rods.
The technical scheme is that a kind of rich CO2The method of Hydrothermal Synthesis Gadolinium monophosphate nanometer rods, under room temperature, prepares Gd respectively3+Salt and PO4 3-Saline solution；It is that 1:1 adds in reactor by above two solution according to volume ratio, adds and stir, and continuously stirred 30min to 1h；Logical CO in reactor2Gas or addition dry ice, in control still, pressure is 1-10MPa, seals autoclave；Heating autoclave, sets reaction temperature as 100-200 DEG C, and persistent period 12h-2d, then natural cooling autoclave is to room temperature；Reacted product is filtered, and priority deionized water and dehydrated alcohol respectively wash, centrifugal twice；Product after washing, be centrifuged is at 50 DEG C～100 DEG C of dry more than 6h；I.e. can get final clean product.
Described Gd3+Salt and PO4 3-Salt is respectively conventional soluble g d3+Salt and solubility PO4 3-Salt.
Beneficial effects of the present invention:
(1) present invention makes full use of CO2The pH of dividing potential drop buffer solution, Gadolinium monophosphate nanometer rods purity height, the size uniform of Hydrothermal Synthesis, crystallization degree is good, controllability is strong.
(2) preparation process of the present invention does not add the Organic substance that surfactant, dispersant, covering etc. not can be recycled, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the Gadolinium monophosphate of embodiment 3 synthesis；
Fig. 2 is the SEM figure of the Gadolinium monophosphate of embodiment 3 synthesis.
Detailed description of the invention
Embodiment 1
Weigh the Gadolinium trinitrate [Gd (NO of certain mass3)3·6H2O] and diammonium phosphate [(NH4)2HPO4], aqueous solution and the aqueous solution of diammonium phosphate of the Gadolinium trinitrate that concentration is 0.36mol/L it is made into respectively with deionized water.Being that 1:1 adds in reactor by Gadolinium trinitrate solution and ammonium dibasic phosphate solution according to volume ratio, add and stir, the initial compactedness of control reactor is 70%, and continuously stirred 30min to 1h.It is filled with 1MPa carbon dioxide to autoclave, closes autoclave.Heating autoclave, controlling reaction temperature is 180 DEG C, and 2 days persistent period, then autoclave naturally cools to room temperature.After reactor pressure release filtering product, be centrifuged, and alternately respectively wash twice with deionized water and dehydrated alcohol the most respectively, relief product is dried 12h under 70 DEG C of environment.
Embodiment 2
Weigh the Gadolinium trinitrate [Gd (NO of certain mass3)3·6H2O] and diammonium phosphate [(NH4)2HPO4], aqueous solution and the aqueous solution of diammonium phosphate of the Gadolinium trinitrate that concentration is 0.36mol/L it is made into respectively with deionized water.Being that 1:1 adds in reactor by Gadolinium trinitrate solution and ammonium dibasic phosphate solution according to volume ratio, add and stir, the initial compactedness of control reactor is 70%, and continuously stirred 30min to 1h.It is filled with 5MPa carbon dioxide to autoclave, closes autoclave.Heating autoclave, controlling reaction temperature is 180 DEG C, and 2 days persistent period, then autoclave naturally cools to room temperature.After reactor pressure release filtering product, be centrifuged, and alternately respectively wash twice with deionized water and dehydrated alcohol the most respectively, relief product is dried 12h under 70 DEG C of environment.
Embodiment 3
Weigh the Gadolinium trinitrate [Gd (NO of certain mass3)3·6H2O] and diammonium phosphate [(NH4)2HPO4], aqueous solution and the aqueous solution of diammonium phosphate of the Gadolinium trinitrate that concentration is 0.36mol/L it is made into respectively with deionized water.By Gadolinium trinitrate solution and diammonium phosphate, (solution is that 1:1 adds in reactor according to volume ratio, adds and stirs, and the initial compactedness of control reactor is 70%, and continuously stirred 30min to 1h.Adding dry ice (drikold) to autoclave, control reacting kettle inner pressure is 10MPa, closes autoclave.Heating autoclave, controlling reaction temperature is 180 DEG C, and 2 days persistent period, then autoclave naturally cools to room temperature.After reactor pressure release filtering product, be centrifuged, and alternately respectively wash twice with deionized water and dehydrated alcohol the most respectively, relief product is dried 12h under 70 DEG C of environment.The product of XRD phenogram display synthesis is pure Gadolinium monophosphate.The Gadolinium monophosphate nanometer rods size uniform of SEM phenogram display synthesis, crystallization degree are good.
Claims (1)
1. a rich CO2The method of Hydrothermal Synthesis Gadolinium monophosphate nanometer rods, it is characterised in that: under room temperature, prepare Gd respectively3+Salt and PO4 3-Saline solution；It is that 1:1 adds in reactor by above two solution according to volume ratio, adds and stir, and continuously stirred 30min to 1h；Logical CO in reactor2Gas or addition dry ice, in control still, pressure is 1-10MPa, seals autoclave；Heating autoclave, sets reaction temperature as 100-200 DEG C, and persistent period 12h-2d, then natural cooling autoclave is to room temperature；Reacted product is filtered, and priority deionized water and dehydrated alcohol respectively wash, centrifugal twice；Product after washing, be centrifuged is at 50 DEG C～100 DEG C of dry more than 6h
, i.e. can get final clean product；Described Gd3+Salt and PO4 3-Salt is respectively soluble g d3+Salt and solubility PO4 3-Salt.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757642A (en) * | 2010-03-03 | 2010-06-30 | 天津科技大学 | Method for preparing gadolinium-containing nano particles |
| CN102534777A (en) * | 2012-02-24 | 2012-07-04 | 南开大学 | Neodymium-doped potassium gadolinium phosphate laser crystal, and preparation method and application thereof |
| CN102849711A (en) * | 2012-08-29 | 2013-01-02 | 深圳大学 | Preparation method of gadolinium phosphate nano-wires |
| WO2014036506A2 (en) * | 2012-09-02 | 2014-03-06 | Global Tungsten & Powders Corp. | Y203:eu having improved brightness at reduced eu weight percentage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757642A (en) * | 2010-03-03 | 2010-06-30 | 天津科技大学 | Method for preparing gadolinium-containing nano particles |
| CN102534777A (en) * | 2012-02-24 | 2012-07-04 | 南开大学 | Neodymium-doped potassium gadolinium phosphate laser crystal, and preparation method and application thereof |
| CN102849711A (en) * | 2012-08-29 | 2013-01-02 | 深圳大学 | Preparation method of gadolinium phosphate nano-wires |
| WO2014036506A2 (en) * | 2012-09-02 | 2014-03-06 | Global Tungsten & Powders Corp. | Y203:eu having improved brightness at reduced eu weight percentage |
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