CN104528681A - Method for CO2-enriched hydro-thermal synthesis of lanthanum phosphate nano-wires - Google Patents
Method for CO2-enriched hydro-thermal synthesis of lanthanum phosphate nano-wires Download PDFInfo
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- CN104528681A CN104528681A CN201410810000.8A CN201410810000A CN104528681A CN 104528681 A CN104528681 A CN 104528681A CN 201410810000 A CN201410810000 A CN 201410810000A CN 104528681 A CN104528681 A CN 104528681A
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- reaction kettle
- room temperature
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- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 11
- 239000002070 nanowire Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 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
- 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
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000000243 solution Substances 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 239000012266 salt solution Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- -1 rare earth phosphate Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000000314 lubricant Substances 0.000 description 1
- 239000008204 material by function Substances 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
- 239000012716 precipitator Substances 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
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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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- Catalysts (AREA)
Abstract
The invention discloses a method for CO2-enriched hydro-thermal synthesis of lanthanum phosphate nano-wires. The method is characterized by comprising the following steps: preparing a La<3+> salt solution and a PO4<3+> salt solution respectively at room temperature; adding the two solutions into a reaction kettle in a volume ratio of 1:1 while stirring, and continuously stirring for 30 minutes to 1 hour; introducing CO2 gas or adding dry ice into the reaction kettle, controlling the pressure in the kettle to be 1-10Mpa, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle, setting the reaction temperature to be 100-200 DEG C and the time of duration to be 12 hours to 2 days, and then naturally cooling the high-pressure reaction kettle to room temperature; filtering a product after reaction, and washing and centrifuging the product twice by using deionized water and anhydrous ethanol successively; and drying the washed and centrifuged product at 50-100 DEG C for more than 6 hours to obtain a final pure product.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth phosphate nanometer material, belong to functional materials synthesis technical field.
Background technology
In the periodic table of elements, lanthanum (La) is positioned at IIIB race, and ordination number is 57, belongs to light rare earths, and the content in the earth's crust is 0.00183%, and content is only second to cerium.In addition, the element of ordination number 58 to 71, they are called as lanthanon together with lanthanum.Lanthanon and yttrium of the same clan (Y) and scandium (Sc) are referred to as rare earth element.Rare earth element has special electron structure (4f
0-145d
0-16s
2), their out-shell electron is substantially identical, internal layer 4f electronic level is very close again, and 4f is the shell of a underfilling, electronic orbit is complete empty, be partly full of and be entirely full of the ion of electronics has optics inertia, for stable state, because of the feature of its outer electronic structure, make it have special physicochemical property.
RE phosphate, because having the advantages such as specific refraction that in good thermostability, water, solubleness is minimum and high, is widely used in the fields such as luminescent material, stupalith, catalyzer, alloy material and lubricant.Lanthanum orthophosphate (LaPO
4), be often used as the good matrix of other rare earth ion of doping.The luminescent material being matrix with nanometer lanthanum orthophosphate have good stability, thermal capacitance large, there is high efficiency feature under the exciting of vacuum-ultraviolet light, excite because material particle size is less than or launches optical wavelength simultaneously, therefore light field can be approximately even in particle range, can significantly improve cathode tube and plasma display sharpness.Meanwhile, lanthanum orthophosphate fusing point is high, with some oxide compound compounds, as Al
2o
3, high temperature resistant, anti-oxidant, that electrical insulating property the is good composite ceramics processed can be prepared.In addition, lanthanum orthophosphate is also widely used in alloy material, catalytic material.Therefore the lanthanum orthophosphate studying controlled monazite structure has great importance.
Current synthesizing rare-earth phosphoric acid salt mainly contains the methods such as sol-gel method, hydrothermal method, the precipitator method, solid phase method, combustion method and microwave method, wherein commonplace with hydrothermal synthesis method.Existing large quantity research shows that pH controls one of most important factor of the brilliant looks of rare earth phosphate nanometer material crystalline form, but adopt the method for Syntheses in water RE phosphate at present, all just in initial aqueous solution, have adjusted pH, there is no buffer pH, lacked the control of gradual change physical and chemical condition to the brilliant looks of its crystalline form, to there is crystallization degree be not very high, particle size be not very evenly, problem that controllability is not strong.At occurring in nature, the geologic fluids that the Ree-phospeate Minerals of hydrothermal origin is formed has certain CO usually
2dividing potential drop, CO in hydrothermal solution
2can the pH of buffered soln.The present invention is by making full use of CO
2the feature of dividing potential drop buffered soln pH, the lanthanum phosphate nano line that Hydrothermal Synthesis purity is high, particle size uniformity, crystallization degree are good, controllability is strong.
Summary of the invention
The technical problem to be solved in the present invention is: provide one to make full use of CO
2the feature of dividing potential drop pH value of buffer solution, the method for the lanthanum phosphate nano line that Hydrothermal Synthesis purity is high, size uniform, crystallization degree are good, controllability is strong.
Technical scheme of the present invention is: a kind of rich CO
2the method of Hydrothermal Synthesis lanthanum phosphate nano line, under room temperature, prepares La respectively
3+salt and PO
4 3+salts solution; Be that 1:1 adds in reactor by above-mentioned two kinds of solution according to volume ratio, add and stir, and Keep agitation 30 min to 1 h; Logical CO in reactor
2gas or add dry ice, controlling still internal pressure is 1-10 Mpa, sealed high pressure reactor; Heating high-pressure reactor, setting temperature of reaction is 100-200 DEG C, time length 12 h-2 d, and then naturally cooling autoclave is to room temperature; Reacted product is filtered, and priority deionized water and dehydrated alcohol respectively wash, centrifugal twice; By washing, centrifugal after product at 50 DEG C ~ 100 DEG C drying 6 more than h, final clean product can be obtained.
Described La
3+salt and PO
4 3+salt is respectively conventional solubility La
3+salt and solubility PO
4 3+salt.
Beneficial effect of the present invention:
(1) the present invention makes full use of CO
2the pH value of dividing potential drop buffered soln, the lanthanum phosphate nano line purity of Hydrothermal Synthesis is high, size uniform, crystallization degree are good, controllability is strong.
(2) organism that tensio-active agent, dispersion agent, coating etc. not can be recycled is not added in preparation process of the present invention, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the lanthanum orthophosphate that embodiment 3 is synthesized;
Fig. 2 is the SEM figure of the lanthanum orthophosphate that embodiment 3 is synthesized.
Embodiment
Embodiment 1
Take the lanthanum nitrate [La (NO of certain mass
3)
36H
2o] and Secondary ammonium phosphate [(NH
4)
2hPO
4], being made into concentration with deionized water is respectively the aqueous solution of the lanthanum nitrate of 0.36mol/L and the aqueous solution of Secondary ammonium phosphate.Be that 1:1 adds in reactor by lanthanum nitrate hexahydrate and ammonium dibasic phosphate solution according to volume ratio, add and stir, the initial compactedness controlling reactor is 70%, and Keep agitation 30 min to 1 h.Be filled with 1 MPa carbon dioxide to autoclave, close autoclave.Heating high-pressure reactor, controlling temperature of reaction is 180 DEG C, and 2 days time length, then autoclave naturally cools to room temperature.After reactor pressure release, product is filtered, centrifugal, and successively alternately respectively to wash twice with deionized water and dehydrated alcohol respectively, most relief product dry 12 h under 70 DEG C of environment.
Embodiment 2
Take the lanthanum nitrate [La (NO of certain mass
3)
36H
2o] and Secondary ammonium phosphate [(NH
4)
2hPO
4], being made into concentration with deionized water is respectively the aqueous solution of the lanthanum nitrate of 0.36mol/L and the aqueous solution of Secondary ammonium phosphate.Be that 1:1 adds in reactor by lanthanum nitrate hexahydrate and ammonium dibasic phosphate solution according to volume ratio, add and stir, the initial compactedness controlling reactor is 70%, and Keep agitation 30 min to 1 h.Be filled with 5 MPa carbon dioxides to autoclave, close autoclave.Heating high-pressure reactor, controlling temperature of reaction is 180 DEG C, and 2 days time length, then autoclave naturally cools to room temperature.After reactor pressure release, product is filtered, centrifugal, and successively alternately respectively to wash twice with deionized water and dehydrated alcohol respectively, most relief product dry 12 h under 70 DEG C of environment.
Embodiment 3
Take the lanthanum nitrate [La (NO of certain mass
3)
36H
2o] and Secondary ammonium phosphate [(NH
4)
2hPO
4], being made into concentration with deionized water is respectively the aqueous solution of the lanthanum nitrate of 0.36mol/L and the aqueous solution of Secondary ammonium phosphate.Be that 1:1 adds in reactor by lanthanum nitrate hexahydrate and ammonium dibasic phosphate solution according to volume ratio, add and stir, the initial compactedness controlling reactor is 70%, and Keep agitation 30 min to 1 h.Add dry ice (solidified carbon dioxide) to autoclave, controlling reacting kettle inner pressure is 10 Mpa, closes autoclave.Heating high-pressure reactor, controlling temperature of reaction is 180 DEG C, and 2 days time length, then autoclave naturally cools to room temperature.After reactor pressure release, product is filtered, centrifugal, and successively alternately respectively to wash twice with deionized water and dehydrated alcohol respectively, most relief product dry 12 h under 70 DEG C of environment.The product of XRD phenogram display synthesis is pure lanthanum orthophosphate.The lanthanum phosphate nano linear dimension of SEM phenogram display synthesis is even, crystallization degree good.
Claims (2)
1. a rich CO
2the method of Hydrothermal Synthesis lanthanum phosphate nano line, is characterized in that: under room temperature, prepares La respectively
3+salt and PO
4 3+salts solution; Be that 1:1 adds in reactor by above-mentioned two kinds of solution according to volume ratio, add and stir, and Keep agitation 30 min to 1 h; Logical CO in reactor
2gas or add dry ice, controlling still internal pressure is 1-10 Mpa, sealed high pressure reactor; Heating high-pressure reactor, setting temperature of reaction is 100-200 DEG C, time length 12 h-2 d, and then naturally cooling autoclave is to room temperature; Reacted product is filtered, and priority deionized water and dehydrated alcohol respectively wash, centrifugal twice; By washing, centrifugal after product at 50 DEG C ~ 100 DEG C drying 6 more than h, final clean product can be obtained.
2. the rich CO of one according to claim 1
2the method of Hydrothermal Synthesis lanthanum phosphate nano line, is characterized in that: described La
3+salt and PO
4 3+salt is respectively conventional solubility La
3+salt and solubility PO
4 3+salt.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410810000.8A CN104528681B (en) | 2014-12-24 | 2014-12-24 | Method for CO2-enriched hydro-thermal synthesis of lanthanum phosphate nano-wires |
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|---|---|---|---|
| CN201410810000.8A CN104528681B (en) | 2014-12-24 | 2014-12-24 | Method for CO2-enriched hydro-thermal synthesis of lanthanum phosphate nano-wires |
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| Publication Number | Publication Date |
|---|---|
| CN104528681A true CN104528681A (en) | 2015-04-22 |
| CN104528681B CN104528681B (en) | 2017-01-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624078A (en) * | 2020-12-24 | 2021-04-09 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity nano lanthanum phosphate powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456714A (en) * | 2003-05-22 | 2003-11-19 | 北京大学 | Method for preparing phosphoric acid rare earth monocrystalline nano-thread |
| CN101058412A (en) * | 2007-05-22 | 2007-10-24 | 同济大学 | Method of greenly preparing rare-earth potassium orthophosphate nano/micro crystal |
| CN102849707A (en) * | 2012-08-29 | 2013-01-02 | 深圳大学 | Preparation method of lanthanum phosphate nano-wires |
-
2014
- 2014-12-24 CN CN201410810000.8A patent/CN104528681B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456714A (en) * | 2003-05-22 | 2003-11-19 | 北京大学 | Method for preparing phosphoric acid rare earth monocrystalline nano-thread |
| CN101058412A (en) * | 2007-05-22 | 2007-10-24 | 同济大学 | Method of greenly preparing rare-earth potassium orthophosphate nano/micro crystal |
| CN102849707A (en) * | 2012-08-29 | 2013-01-02 | 深圳大学 | Preparation method of lanthanum phosphate nano-wires |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624078A (en) * | 2020-12-24 | 2021-04-09 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity nano lanthanum phosphate powder |
| CN112624078B (en) * | 2020-12-24 | 2023-05-16 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity nano lanthanum phosphate powder |
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