CN1974885A - Low temperature process of preparing RE borate crystal with oxide as precursor - Google Patents
Low temperature process of preparing RE borate crystal with oxide as precursor Download PDFInfo
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- CN1974885A CN1974885A CN 200610118343 CN200610118343A CN1974885A CN 1974885 A CN1974885 A CN 1974885A CN 200610118343 CN200610118343 CN 200610118343 CN 200610118343 A CN200610118343 A CN 200610118343A CN 1974885 A CN1974885 A CN 1974885A
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Abstract
The present invention belongs to the field of micron/nanometer material preparing technology and hydrothermal synthesis technology, and is especially low temperature process of preparing RE borate crystal with oxide as precursor. In the hydrothermal system, insoluble RE oxide and hydrated boron trioxide or boron trioxide as the boron source and precursor are reacted at 190-280 deg.c for 12-48 hr, and through further washing, the required RE borate crystal is obtained. The present invention provides one inorganic synthesis way, and the production process has no any pollution. The present invention has simple technological process, easy-to-constitute reaction system, high product purity and other advantages, and is suitable for industrial production.
Description
Technical field
The invention belongs to the synthetic field of micro-/ nano material preparation technology and hydro-thermal, being specifically related under a kind of low temperature with the oxide compound is the method that presoma prepares RE borate crystal.
Background technology
Rare earth element is because of its distinctive 4f layer electronic structure, and exciting light is the premium properties of line spectrum or narrow-band spectrum, gains great popularity in fluorescent material.Fluorescent RE powder will replace zinc, strontium, sulphide fluorescent material, to obtain higher brightness and sharpness.The RE(rare earth) borate series phosphor powder is the end of the nineties, in order to adapt to the development of large-screen high-resolution color projection TV and terminal technique of display, and the novel rare-earth luminescent material of researching and developing of a class.RE(rare earth) borate also is widely used in multiple fluorescent glass, photodiode, the preparation of optical materials such as nonlinear optical material, laserable material, magneticsubstance, the raw material of the additive of lubrication oil antiwear antifriction etc. simultaneously.Along with the development of nanotechnology, to the demand of nano-scale rare earth orthoboric acid salt with increasing.Yet the report about the preparation of nano level rare earth orthoboric acid salt but very lacks, this may since RE(rare earth) borate be more difficult to get under the common condition relevant: because under normal temperature or medium temperature condition, solid boric acid and rare earth oxide can not react; If in the aqueous solution, utilize rare earth salts and borate effect, borate hydrate generally forms (synthetic method mainly adopts solution method or hydrothermal method) under slightly acidic, neutrality or alkaline condition and trivalent rare earth ions hydrolysis proneness under this synthesis condition is bigger, thereby also is difficult to form the hydrated rare-earth borate.In recent years, the preparation method of the rare earth orthoboric acid salt of having reported mainly is confined to solid phase method and sol-gel method: solid phase method is the boron source with excessive borate or boric acid or boron simple substance normally, with rare earth oxide or salt is cationic source, method by high-temperature calcination (＞600 ℃) obtains corresponding crystal, sol-gel method mainly is to utilize organic boron oxide compound to be borate roc source, with organic rare earth compounds or rare earth salts is that cationic source forms colloidal sol under the effect of organic solvent or glue crosslinking agent, and then formation gel, remove organic composition by the agglomerating method at last, and obtain mutually deserved nano-scale rare earth borate.
Though above-mentioned these methods provide some synthesizing rare-earths boratory approach, still there is deficiency, to pass through high temperature as solid state reaction, excessive boron and complicated step could obtain the nano level borate; And sol-gel can cause a large amount of organic wastes, and production cost is higher, also can produce a large amount of waste gas simultaneously, is unfavorable for environment protection and reasonable resources application.
Summary of the invention
The objective of the invention is to propose that a kind of controllable granularity, crystal with controllable crystal forms, high purity, processing are convenient, to be easy under the industrialized low temperature with the oxide compound be the method that presoma prepares RE borate crystal.
Be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature that the present invention proposes, its concrete steps are as follows:
(1) be presoma with boron source and rare earth oxide, with the deionized water is solvent, place pressure vessel (as reactor) respectively, mix, wherein, the mol ratio of boron source and rare earth oxide is 1: 1-1.2: 1, and the ratio of deionized water and rare earth oxide amount of substance is 250: 1-400: 1, the add-on of deionized water is the 50%-80% of container volume;
(2) container that compound is housed in the step (1) is placed the temperature control kiln roasting, with 8.5-11.5 ℃ of/minute intensification speed, according to obtaining the requirement of different qualities product, temperature is 190 ℃-280 ℃ in the control stove, thermostatically heating 12-48 hour, take out container, naturally cool to room temperature;
(3) with the precipitated product washing of gained in the container in the step (2), promptly get desired product;
Wherein, described boron source is hydration boron trioxide or boron trioxide; Described rare earth oxide is all divalence, trivalent, quaternary rare-earth oxide and hydrates thereof, and purity all is not less than chemical pure.
Among the present invention, step can also add additive in (1), and the add-on of additive is that the mol ratio of additive and rare earth oxide is 0.1: 1-1: 1.
Among the present invention, described additive is the one to multiple kind in inorganic part, organic ligand or the tensio-active agent etc.
Among the present invention, described organic ligand can adopt EDTA and salt, citric acid and salt thereof, adjacent phenanthroline, phenanthroline, quadrol and multidentate ligands such as derivative, phosphoric acid ester thereof; Tensio-active agent can adopt anion surfactant, long-chain phosphoric acid ester etc.; Cation form and promoting agent can adopt long-chain fat ammonium salt or imidazole salts etc.; Nonionogenic tenside can adopt polyoxyethylene glycol, cyclodextrin, polyphenyl ethylene glycol, POLYPROPYLENE GLYCOL etc.
Among the present invention, step mixes in (1), can be undertaken by modes such as mechanical stirring or vibration, magnetic agitation, sonic oscillations.
Among the present invention, the described sonic oscillation time is 8-15 minute.
Among the present invention, the alternately washing of employing deionized water of washing described in the step (3) and dehydrated alcohol, washing times is 3-6 time, after each washing is finished, with wash after the centrifuge separator separation next time again.
Utilize RE borate crystal that the inventive method prepares in the powder of vacuum ultraviolet (VUV) fluorescent material, fluorescent glass, magneto-optic memory technique, piezoelectric ceramics, photoelectric ceramics, photorectifier, transmitter, electrode or the application in the bulk material.
Structure, pattern, composition to the inventive method products therefrom characterize, can select X-ray powder diffraction (XRD), scanning electronic microscope (SEM), fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS), transmission electricity border (TEM) etc. respectively for use, XRD result shows number, size-grade distribution and the main component of the crystal formation kind of product, SEM, TEM shows particle diameter and whole pattern, the result of FTIR checking XRD and the content of moisture.It is elementary composition that XPS detects microcell, the result of evidence XRD.
The invention has the advantages that:
1. the present invention has realized utilizing the oxide compound that is insoluble in water under the normal temperature presoma for hydro-thermal reaction, breaks through water synthetic classical mode in the past, is inorganic synthetic a kind of new route of synthesis that provides.
2. the present invention adopts the presoma of oxide compound for reaction, used salts reaction thing different from the past, in preparation process, can not produce the by product that pollution is arranged to environment, atom utilization can reach 100% in theory, be that whole process of production does not have any pollution, meeting the Sustainable development requirement, is a kind of environment-friendly type synthetic method.
3. method used in the present invention is a hydrothermal method, and it is simple to have equipment, and operation is convenient, is convenient to industry and transforms, and realizes scale operation.
4. the present invention is applied widely, can be used for all RE borate crystals and comprise the synthetic of nano/micron level powder, by changing the temperature and time of reaction, the kind of additive can be regulated and control crystal formation, pattern, the particulate size of product, thereby the nano level that obtains different-shape is to the micron order crystal.Gained nanometer-size die particle size range is 40-100nm, and length-to-diameter ratio is 1-30; Under the condition of reaction times, can make the micron order crystal grain of particle diameter＞1 μ m than length.The inventive method can be prepared the product of different size easily, to satisfy the requirement of various processes.
5. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, and product pattern, size are easily controlled, and purity height, better crystallinity degree and product are handled convenient succinct, are suitable for large-scale commercial production.
6. the portion of product of the present invention's preparation has the physicals of aspects such as good light, electricity, magnetic, can be used as the vacuum ultraviolet (VUV) fluorescent material, fluorescent glass, the powder of magneto-optic memory technique, piezoelectric ceramics, photoelectric ceramics, photorectifier, transmitter, electrode or bulk material have comparatively vast potential for future development and application space.
The present invention adopts comparatively sophisticated hydro-thermal synthetic system, directly is that reactant is realized with the oxide compound.The hydro-thermal synthetic system is a kind of comparatively sophisticated nanocrystal preparation method, compare with other wet chemical methods such as sol-gel method, coprecipitation methods, it is good that it has a product crystal formation, the characteristics that particle-size distribution is narrow, easy to operate, do not need special conditionss such as High Temperature High Pressure have been widely used in the preparation of monocrystalline, polycrystalline, nano level simple substance and inorganic/inorganic-organic compound (compound) thing.It is that rare earth ion source and hydration boron trioxide or boron trioxide are prepared for the boron source and had the nanocrystalline of regular morphology and crystal formation and/or micron order crystal that the presoma of the present invention reaction is selected rare-earth oxide.The kind of the temperature of the present invention by conditioned reaction, time, additive and consumption are realized the control to crystal formation and pattern.
Description of drawings
Fig. 1 is 200 ℃ of XRD spectra of descending the RE(rare earth) borate for preparing under the same terms of 24 hours of reaction.
Fig. 2 is the 280 ℃ of yttrium borate descending to react to obtain in 24 hours and the XRD spectra of boric acid erbium.
Fig. 3 is 240 ℃ and reacts the XRD spectra that obtained the boric acid lanthanum in 24 hours down.
Fig. 4 is 220 ℃ of XRD spectra of reacting the borate doped lanthanum of dysprosium that obtained in 24 hours down.
Fig. 5 is 200 ℃ of XRD spectra of reacting the boric acid neodymium that obtained in 12 hours down.
Fig. 6 is 200 ℃ of TEM photos that react the RE(rare earth) borate that obtained preparing in 24 hours down.Wherein, A is GdBO
3The TEM photo, B is DyBO
3The TEM photo, C is NdBO
3The TEM photo, D is LaBO
3The TEM photo, E is SmBO
3The TEM photo.
Fig. 7 is the 280 ℃ of yttrium borate descending to react to obtain in 24 hours and the TEM photo of boric acid erbium.Wherein, A is ErBO
3The TEM photo, B is YBO
3The TEM photo.
Fig. 8 be 220 ℃ down the borate doped lanthanums of 2.5% dysprosium that obtained in 24 hours of reaction the TEM photo.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1: preparation boric acid lanthanum
Be respectively in the tetrafluoroethylene reactor of 10ml to two volumes, add 2.0 * 10 respectively
-4The La of mol
2O
3, 2.0-2.2 * 10
-4The B of mol
2O
3, closed reactor behind the 7ml deionized water, two reactors are transferred in the ultra-sonic generator, all sonic oscillation is 10 minutes, the reactor that mixed solution will be housed then is transferred to the temperature control kiln roasting respectively, heat-up rate with 10 ℃/minute, control reaction in furnace temperature is respectively 200 ℃, 240 ℃, be 24 hours between thermostatically heating, take out reactor, naturally cool to room temperature, take out gained precipitated product in the reactor respectively, alternately wash respectively 3 times, promptly get desired product with deionized water and dehydrated alcohol.
LaBO among Fig. 1
3Curve be LaBO
3The X-ray powder diffraction collection of illustrative plates.Products obtained therefrom is consistent with the standard spectrogram of the boric acid lanthanum of rhombic system, and broadening in various degree occurred, shows that product is the nano level particle of monocrystalline attitude.The TEM photo of product further confirms it is nano level bar-like single crystal from Fig. 6 (D).
Fig. 3 provides the X-ray powder diffraction collection of illustrative plates of products obtained therefrom under 240 ℃ of reaction conditionss.Can products obtained therefrom from figure all consistent with the standard spectrogram of the boric acid lanthanum of rhombic system, and broadening has in various degree appearred, show that product is the nano level particle of monocrystalline attitude.The TEM photo of product further confirms it is nano level bar-like single crystal from Fig. 6 (D).
Embodiment 2: the borate of preparation Sm, Gd, Dy
Be respectively in the tetrafluoroethylene reactor of 10ml to three volumes, add 2.0 * 10 respectively
-4The Sm of mol
2O
3, Gd
2O
3, Dy
2O
3And 2.0-2.2 * 10
-4Mol B
2O
3-3H
2O is a raw material, closed reactor behind the deionized water 6-7mL, mix, three reactors that mixed solution will be housed then are transferred to the temperature control kiln roasting respectively, and control reaction in furnace temperature is respectively 200 ℃, the thermostatically heating time is 24 hours, take out reactor, naturally cool to room temperature, take out gained precipitation in the reactor respectively, alternately wash 4-5 time respectively, promptly get desired product with deionized water and dehydrated alcohol.
The SmBO that provides among Fig. 1
3Curve be products obtained therefrom SmBO
3X ray diffracting spectrum, find consistent by retrieval with the standard spectrogram.Tangible broadening phenomenon appears in spectrogram, shows that product is nano level particle.It is nano level tabular crystal that the TEM photo of the product that provides among Fig. 6 (E) further confirms.
The GdBO that provides among Fig. 1
3Curve be products obtained therefrom GdBO
3X ray diffracting spectrum, find consistent by retrieval with the standard spectrogram.Tangible broadening phenomenon appears in spectrogram, shows that product is nano level particle.It is nano level tabular crystal that the TEM photo of the product that provides among Fig. 6 (A) further confirms.
The DyBO that provides among Fig. 1
3Curve be products obtained therefrom DyBO
3X ray diffracting spectrum, find consistent by retrieval with the standard spectrogram.Tangible broadening phenomenon appears in spectrogram, shows that product is nano level particle.It is nano level tabular crystal that the TEM of the product that provides among Fig. 6 (B) further confirms.
Embodiment 3: the orthoboric acid salt of preparation Er and Y
Be respectively in the tetrafluoroethylene reactor of 10ml to two volumes, add 2.0 * 10 respectively
-4The Er of mol
2O
3, Y
2O
3, 2.0-2.2 * 10
-4Mol B
2O
3Be raw material, deionized water 7-8mL, additive phenanthroline are 0.02 gram back closed reactor, mix, two reactors that mixed solution will be housed then are transferred to the temperature control kiln roasting respectively, control reaction in furnace temperature is 280 ℃, and the reaction times is 24 hours, takes out reactor, naturally cool to room temperature, take out gained precipitation in the reactor respectively, alternately wash 5-6 time respectively, promptly get desired product with deionized water and dehydrated alcohol.
Provided ErBO among Fig. 2
3Curve be ErBO
3X ray diffracting spectrum, find that by retrieval product is consistent with boric acid erbium standard spectrogram, tangible broadening phenomenon appears in spectrogram, the ErBO that provides among Fig. 7 (A)
3The TEM photo, show that product is nano level tabular crystal.
Provided YBO among Fig. 2
3Curve be YBO
3X ray diffracting spectrum, find that by retrieval product is consistent with boric acid erbium standard spectrogram, tangible broadening phenomenon appears in spectrogram, the YBO that provides among Fig. 7 (B)
3The TEM photo, show that product is nano level tabular crystal.
To volume is in the tetrafluoroethylene reactor of 10ml, adds 2.0 * 10 respectively
-4(1-x) La of mol
2O
3+ x Dy
2O
3(x＜12.5%), 2.0-2.2 * 10
-4Mol B
2O
3Be raw material, closed reactor behind the deionized water 6-7mL, mix, the reactor that mixed solution will be housed then is transferred to the temperature control kiln roasting, and control reaction in furnace temperature is 220 ℃, reaction times is 24 hours, take out reactor, naturally cool to room temperature, take out gained precipitation in the reactor, alternately wash 5-6 time respectively, promptly get desired product with deionized water and dehydrated alcohol.
The X ray diffracting spectrum of the products obtained therefrom that provides among Fig. 4 finds that by retrieval product is consistent with boric acid lanthanum standard standard spectrogram.Tangible broadening phenomenon appears in spectrogram, shows that product is nano level particle.Fig. 8 provides the TEM photo of products obtained therefrom, shows that product is nano level tabular crystal.
Embodiment 5, preparation boric acid neodymium
To volume is in the tetrafluoroethylene reactor of 10ml, adds 2.0 * 10 respectively
-4The Nd of mol
2O
3, 2.0-2.2 * 10
-4Mol B
2O
3Be raw material, deionized water 6-7mL, closed reactor mixes, the reactor that mixed solution will be housed then is transferred to the temperature control kiln roasting, control reaction in furnace temperature is 200 ℃, and the reaction times is 12 hours, takes out reactor, naturally cool to room temperature, take out gained precipitation in the reactor, alternately wash 3-6 time respectively, promptly get desired product with deionized water and dehydrated alcohol.The X ray diffracting spectrum of the products obtained therefrom that provides from Fig. 5, by the boric acid samarium standard spectrogram basically identical of retrieval this product of discovery and hexagonal system, the material that shows gained is the boric acid neodymium of hexagonal system.Tangible broadening phenomenon appears in spectrogram, shows that product is nano level tabular crystal.
Claims (7)
1, be the method that presoma prepares RE borate crystal with the oxide compound under a kind of low temperature, it is characterized in that concrete steps are as follows:
(1) be presoma with boron source and rare earth oxide, with the deionized water is solvent, place container respectively, mix, wherein, the mol ratio of boron source and rare earth oxide is 1: 1-1.2: 1, and deionized water is 250 with the ratio of rare earth oxide amount of substance: 1-400: 1, the add-on of deionized water is the 50%-80% of container volume;
(2) container that compound is housed in the step (1) is placed the temperature control kiln roasting, with 8.5-11.5 ℃ of/minute intensification speed, according to obtaining the requirement of different qualities product, temperature is 190 ℃-280 ℃ in the control stove, thermostatically heating 12-48 hour, take out container, naturally cool to room temperature;
(3) with the precipitated product washing of gained in the container in the step (2), promptly get desired product;
Wherein, described boron source is hydration boron trioxide or boron trioxide; Described rare earth oxide is all divalence, trivalent, quaternary rare-earth oxide and hydrates thereof.
2, be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature according to claim 1, it is characterized in that also adding additive in step (1), the add-on of additive is that the mol ratio of additive and rare earth oxide is 0.1: 1-1: 1.
3, be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature according to claim 2, it is characterized in that described additive is the one to multiple kind in inorganic part, organic ligand or the tensio-active agent.
4, be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature according to claim 1 and 2, it is characterized in that mixing in the step (1), undertaken by mechanical stirring or vibration, magnetic agitation, sonic oscillation mode.
5, be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature according to claim 4, it is characterized in that the described sonic oscillation time is 8-15 minute.
6, be the method that presoma prepares RE borate crystal with the oxide compound under the low temperature according to claim 1 and 2, it is characterized in that the alternately washing of employing deionized water of washing described in the step (3) and dehydrated alcohol, washing times is 3-6 time, after each washing is finished, with wash again after the centrifuge separator separation next time.
7, the RE borate crystal that obtains of a kind of preparation method as claimed in claim 1 or 2 is in the powder of vacuum ultraviolet (VUV) fluorescent material, fluorescent glass, magneto-optic memory technique, piezoelectric ceramics, photoelectric ceramics, photorectifier, transmitter, electrode or the application in the bulk material.
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| CN105694873A (en) * | 2016-03-29 | 2016-06-22 | 陕西师范大学 | Method for preparing InBO3:Eu<3+> luminescent material by adopting boric acid melting process |
| CN105694874A (en) * | 2016-03-29 | 2016-06-22 | 陕西师范大学 | Preparation method of polyhedral InBO3:Eu<3+> luminescent material |
| CN106118655A (en) * | 2016-06-16 | 2016-11-16 | 沈阳化工大学 | A kind of preparation method of the rare earth ion doped controllable luminous powder of lanthanum borate crystalline phase |
| CN106283175A (en) * | 2016-09-22 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3o5, CsB3o5and CsLiB6o10method |
| CN109019656A (en) * | 2018-09-28 | 2018-12-18 | 包头稀土研究院 | The production method of nano rareearth oxidate powder body |
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Family Cites Families (2)
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| JP2005298272A (en) * | 2004-04-12 | 2005-10-27 | Fuji Photo Film Co Ltd | Method of manufacturing rare-earth borate |
| JP2005298679A (en) * | 2004-04-12 | 2005-10-27 | Fuji Photo Film Co Ltd | Method for producing rare earth element borate |
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| CN105694873A (en) * | 2016-03-29 | 2016-06-22 | 陕西师范大学 | Method for preparing InBO3:Eu<3+> luminescent material by adopting boric acid melting process |
| CN105694874A (en) * | 2016-03-29 | 2016-06-22 | 陕西师范大学 | Preparation method of polyhedral InBO3:Eu<3+> luminescent material |
| CN105694874B (en) * | 2016-03-29 | 2018-03-06 | 陕西师范大学 | A kind of polyhedral InBO3:Eu3+The preparation method of luminescent material |
| CN106118655A (en) * | 2016-06-16 | 2016-11-16 | 沈阳化工大学 | A kind of preparation method of the rare earth ion doped controllable luminous powder of lanthanum borate crystalline phase |
| CN106118655B (en) * | 2016-06-16 | 2019-04-19 | 沈阳化工大学 | A kind of preparation method of the rare earth ion doped controllable luminous powder of lanthanum borate crystal phase |
| CN106283175A (en) * | 2016-09-22 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3o5, CsB3o5and CsLiB6o10method |
| CN106283175B (en) * | 2016-09-22 | 2018-08-24 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3O5、CsB3O5And CsLiB6O10Method |
| CN109019656A (en) * | 2018-09-28 | 2018-12-18 | 包头稀土研究院 | The production method of nano rareearth oxidate powder body |
| CN109473674A (en) * | 2018-12-16 | 2019-03-15 | 成都其其小数科技有限公司 | A kind of graphene-supported nanometer LiNiPO anode material of lithium battery and preparation method |
| CN109473674B (en) * | 2018-12-16 | 2020-09-18 | 河南英能新材料科技有限公司 | Graphene-loaded nano nickel phosphate lithium battery positive electrode material and preparation method thereof |
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