CN106588964B - A kind of rare earth compounding nano material and its preparation method and application - Google Patents
A kind of rare earth compounding nano material and its preparation method and application Download PDFInfo
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- CN106588964B CN106588964B CN201611094713.4A CN201611094713A CN106588964B CN 106588964 B CN106588964 B CN 106588964B CN 201611094713 A CN201611094713 A CN 201611094713A CN 106588964 B CN106588964 B CN 106588964B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of rare earth compounding nano materials and its preparation method and application, the rare earth compounding nano material the preparation method is as follows: using ethyl alcohol and water mixed solution as reaction medium, Pyromellitic Acid and inorganic salts are raw material, triethylamine is regulator, and a variety of rare earth compounding nano materials have been made.The appearance of nano material is uniform, and size and shape can be adjusted by different demands, is easy to disperse in water, ethyl alcohol, DMF etc., solves the problems, such as that nano material is not easy to disperse.Preparation method simple and the characteristics of be easily dispersed, makes it have the potential quality of industrial application.Using rare earth and doping type rare earth compounding as presoma, by air high-temperature calcination, it is prepared for that there is the nanometer rare earth oxide material similar with presoma.The method can control the morphology and size of rare earth oxide by complex precursors, realize the uniform compound of oxide, and preparation process is simple, be not necessarily to expensive device, and raw material is cheap and easy to get.
Description
Technical field
The preparation for the organic inorganic hybridization rare earth compounding nano material with good dispersion that the present invention relates to a kind of with
And rare earth, the preparation of composite rare-earth oxide nano material, belong to nano material synthesis field.
Background technique
Rare earth usually enjoys the laudatory title of " industrial monosodium glutamate ", and new material and high-technology field have pole to rare earth in recent years
Big demand.There are more strict requirements in different applications to the particle size distribution of rare earth powder, and this requires me
Be dedicated to the synthesis technology of exploratory development rare earth material.
The special excellent properties that there are nano material many traditional materials not have, such as small-size effect, surface effect
It answers, macro quanta tunnel effect etc., thus the study on the synthesis of nano material is concerned.Preparation method has very much, and total comes
It says and is divided into two major classes, is i.e. physical method and chemical method, wherein physical method includes comminuting method, vacuum deposition method, sputtering method, gas
Evacuator body method etc., chemical method include gas-phase decomposition method, the precipitation method, spray-on process, sol-gal process, hydro-thermal method etc..
2010, related application (102531022 A of Chinese patent CN), which is reported, prepared list by precipitating reagent of urea
Disperse nanometer rare earth oxide ball, needs to be added exhibiting high surface activated polyethylene pyrrolidones in synthesis process.2012, have
Patent (102730738 A of Chinese patent CN), which is reported, to be smelted into alloy as raw material using rare earth metal and prepares binary or polynary dilute
The method of native oxide nano particles.This method complex process needs higher reaction temperature, and energy consumption is high, and equipment cost is high.
2010, there is patent application (101857192 A of Chinese patent CN) to report sol-gel method and prepare titanium/rare earth hybrid nanometer
Material.This method is needed using a large amount of organic gel agent, and entire sol-gel process needs the long period, and technique is multiple
It is miscellaneous.
The present invention is prepared for the uniform rare earth compounding nano material of appearance and size by easy complexed-precipitation method.Nanometer
One of key problem in technology of the material application i.e. dispersion of material.Due to high specific surface area and high surface energy, nano material is held very much
It is easy to reunite, to lose its due property.Thus have to that nano particle is allowed to be uniformly dispersed in practical applications
In system, the phenomenon that overcoming nanoparticle agglomerates.Direct precipitation method is to prepare nano material method the easiest, but this method
Nano material obtained cannot obtain evenly dispersed material due to agglomeration.
Summary of the invention
The present invention provides a kind of simple preparation method of organic inorganic hybridization rare earth compounding nano material, the preparation sides
Method simple process, it is high-efficient；Obtained product has good dispersion performance in water, ethyl alcohol, DMF equal solvent.
The present invention also provides a kind of using rare earth compounding as the method for precursor preparation nanometer rare earth oxide material, obtains
The uniform doping of the oxide arrived, granularity are uniform.
A kind of preparation method of rare earth compounding nano material, comprising the following steps:
In the in the mixed solvent of second alcohol and water, using triethylamine as regulator, using Pyromellitic Acid and inorganic salts as raw material into
Row complex reaction, after reaction by being centrifuged and being dried to obtain the rare earth compounding nano material.
Rare earth compounding appearance of nano material made from complexed-precipitation method through the invention is uniform, and (nanometer is to micro- for size
Rice) and pattern (particle, rodlike, sheet material) be adjusted on demand.Also, granular material obtained is easy in water, ethyl alcohol, DMF
Disperse in equal solvent.The preparation method of the rare earth compounding nano material has many advantages, such as that such as product particle degree obtained is uniform,
Preparation process is simple, high-efficient, is not necessarily to high temperature and pressure, the equipment for not needing valuableness, and required raw material is cheap and easy to get etc..
Preferably, the inorganic salts are the one or more or inorganic salt of rare earth of inorganic salt of rare earth and transition gold
Belong to the combination of inorganic salts.
Preferably, the inorganic salt of rare earth is scandium salts, yttrium salt, lanthanum salt, cerium salt, praseodymium salt, neodymium salt, promethium salt, samarium salt, europium
One or more of salt, gadolinium salt, terbium salt, dysprosium salt, holmium salt, erbium salt, thulium salt, ytterbium salt, lutetium salt.
Other than the inorganic salt of rare earth of one-component, the rare earth that inorganic salt raw material is also possible to hybrid transition metal salt is inorganic
Salt or two kinds and two or more inorganic salt of rare earth mixtures.Preferably, the transition metal inorganic salts are titanium
One or more of salt, vanadic salts, chromic salts, manganese salt, molysite, cobalt salt, nickel salt, mantoquita.
Preferably, the volume ratio of the second alcohol and water is 1:0.9~1.1；
The mole dosage ratio of the Pyromellitic Acid and inorganic salts is 1:0.9~1.1.
Preferably, the temperature of the complex reaction is 70~90 DEG C.
The present invention also provides the rare earth compounding nano materials that the preparation method described in one kind obtains.
Meanwhile using rare earth compounding of the invention as presoma, by the simple process of air high-temperature calcination, can prepare
Rare earth compounding presoma has the rare earth oxide and composite rare-earth oxide nano material of similar pattern.
The present invention also provides a kind of preparation method of rare earth oxide, the rare earth compounding nano material is in air
In calcined, obtain affiliated rare earth oxide.
The advantages of the method is the morphology and size that rare earth oxide can be adjusted by rare earth compounding presoma, can
To realize the Uniform Doped of oxide, product particle degree obtained is uniform, and simple process is efficient, is not necessarily to expensive device.
Preferably, the temperature of calcining is 600~700 DEG C, calcination time is 1~5h.
The present invention also provides a kind of rare earth oxides, are obtained by the preparation method；
The rare earth oxide is single rare earth oxide or composite rare-earth oxide.Obtained single rare earth oxidation
Object includes Sc2O3, Y2O3, La2O3, CeO2, Pr6O11, Nd2O3, Pm2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3,
Er2O3, Tm2O3, Yb2O3, Lu2O3；Composite rare-earth oxide includes that titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper are transient metal doped
Rare earth oxide, and two kinds and the compound oxide-based nanomaterial of two or more rare earths.
Compared with existing nano material synthetic technology, synthetic method of this invention has that process flow is simple, condition
Mildly, at low cost, the advantages that pattern of nano material is uniform, and size can regulate and control on demand.The invention achievement is for rare earth in industry
Exhaust gas and vehicle maintenance service, petroleum cracking, battery electrode material, luminescent material, electromagnetic shielding, ultraviolet radiation preventing, rare earth
The application of the industries such as filling-modified polymer is significantly.
Detailed description of the invention
Fig. 1 is the cupric oxide doped cerium oxide nano sheet material that embodiment 6 obtains.
Specific embodiment
Embodiment 1
A method of organic-inorganic hybrid nano material is synthesized with Pyromellitic Acid and gadolinium salt.Weigh the equal benzene of 0.1272g
Tetracarboxylic acid and 0.1762g gadolinium acetate hydrate dissolve in 10mL second alcohol and water respectively, and 80 DEG C of reaction 1h after mixing finally will be anti-
Object centrifuge dripping is answered, 50 DEG C of convection ovens dryings is placed in, obtains about 5 microns of length of rod-like nano material, yield 72%.
Embodiment 2
A method of organic-inorganic hybrid nano material is synthesized with Pyromellitic Acid and gadolinium salt.Weigh the equal benzene of 0.1272g
Tetracarboxylic acid and 0.1762g gadolinium acetate hydrate dissolve in 10mL second alcohol and water respectively, and the three of 40 microlitres are added in ethanol solution
Ethamine, 80 DEG C of reaction 1h after mixing are placed in 50 DEG C of convection ovens dryings, obtain partial size 300 finally by reactant centrifuge dripping
~400 nanometers of rare earth Gd coordination compound particle, yield 74%.
Embodiment 3
A method of organic-inorganic hybrid nano material is synthesized with Pyromellitic Acid and gadolinium salt.Weigh the equal benzene of 0.1272g
Tetracarboxylic acid and 0.1762g gadolinium acetate hydrate dissolve in 10mL second alcohol and water respectively, and 100 microlitres are added in ethanol solution
Triethylamine, 80 DEG C of reaction 1h after mixing are placed in 50 DEG C of convection ovens dryings, obtain partial size and exist finally by reactant centrifuge dripping
200~300 nanometers of rare earth Gd coordination compound particle, yield 75%.Nano particle easily disperses in water, ethyl alcohol, DMF, about
4mg/mL suspension, which is placed three days, does not occur obvious sediment.
Embodiment 4
For one kind with Pyromellitic Acid, the rare earth cerium salt for mixing transition metal mantoquita is Material synthesis organic-inorganic hybrid nanometer
The method of material.Weigh three kinds of 0.3180g Pyromellitic Acid, 0.3770g cerous acetate hydrate and 0.0250g acetic acid copper hydrate
Inorganic salts, Pyromellitic Acid and inorganic salts are dissolved in respectively in 25mL second alcohol and water, 80 DEG C of reaction 1h after mixing, then will reaction
Object centrifuge dripping is placed in 50 DEG C of convection ovens dryings, obtains thickness in the Nano sheet material of 100 rans, yield is 71%.
Embodiment 5
A method of using rare earth compounding as precursor preparation pure rare earth oxide-based nanomaterial.What embodiment 3 obtained
Gadolinium rare earth compounding in air 650 DEG C of calcining 2h up to gadolinium oxide nano material, yield: 87%.Nanometer rare earth oxide material
Material has similar pattern with rare earth compounding presoma, is gadolinium oxide particle of the partial size at 200~300 nanometers.
Embodiment 6
A method of using rare earth compounding as precursor preparation composite rare-earth oxide nano material.Embodiment 4 obtains
Complex precursors in air 650 DEG C of calcining 2h up to cupric oxide doped cerium oxide nano materials, yield: 89%.It is multiple
Closing nanometer rare earth oxide material has similar pattern with its complex precursors, and specific structure is shown in Fig. 1.
Claims (5)
1. a kind of preparation method of rare earth compounding nano material, which comprises the following steps:
In the in the mixed solvent of second alcohol and water, using triethylamine as regulator, network is carried out using Pyromellitic Acid and inorganic salts as raw material
Reaction is closed, after reaction by being centrifuged and being dried to obtain the rare earth compounding nano material；
The inorganic salts are gadolinium salt.
2. the preparation method of rare earth compounding nano material according to claim 1, which is characterized in that the ethyl alcohol and
The volume ratio of water is 1:0.9~1.1；
The mole dosage ratio of the Pyromellitic Acid and inorganic salts is 1:0.9~1.1.
3. the preparation method of rare earth compounding nano material according to claim 1, which is characterized in that the complexing is anti-
The temperature answered is 70~90 DEG C.
4. a kind of preparation method of rare earth oxide characterized by comprising
(1) rare earth compounding nano material is obtained according to the described in any item methods of claims 1 to 3；
(2) the rare earth compounding nano material that step (1) obtains is calcined in air, obtains the rare-earth oxidation
Object.
5. the preparation method of rare earth oxide according to claim 4, which is characterized in that the temperature of calcining is 600~700
DEG C, calcination time is 1~5h.
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| CN107602377B (en) * | 2017-09-04 | 2021-02-09 | 天津城建大学 | Preparation method of p-hydroxybenzoic acid rare earth complex nano-microspheres |
| CN108855070A (en) * | 2018-06-20 | 2018-11-23 | 杭州同久净颢科技有限责任公司 | A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351235A (en) * | 2009-05-08 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Rare earth complex, rare earth oxide and preparation method thereof |
| CN106317092A (en) * | 2016-08-19 | 2017-01-11 | 安阳师范学院 | Europium complex of pyromellitic acid ligand as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351235A (en) * | 2009-05-08 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Rare earth complex, rare earth oxide and preparation method thereof |
| CN106317092A (en) * | 2016-08-19 | 2017-01-11 | 安阳师范学院 | Europium complex of pyromellitic acid ligand as well as preparation method and application thereof |
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