CN106745172A - A kind of rare earth hydroxycarbonate LnOHCO3The preparation method of ultrathin nanometer band - Google Patents
A kind of rare earth hydroxycarbonate LnOHCO3The preparation method of ultrathin nanometer band Download PDFInfo
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- CN106745172A CN106745172A CN201611222860.5A CN201611222860A CN106745172A CN 106745172 A CN106745172 A CN 106745172A CN 201611222860 A CN201611222860 A CN 201611222860A CN 106745172 A CN106745172 A CN 106745172A
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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
- C01F17/247—Carbonates
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/30—Three-dimensional structures
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- 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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- 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
- C01P2004/17—Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer
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Abstract
Rare earth hydroxycarbonate LnOHCO is prepared the present invention relates to one kind3The method of ultrathin nanometer band, comprises the following steps：（1）The mixed solution that acetic acid rare-earth salts, urea are dissolved in oleyl amine and ethanol is stirred to form suspension at room temperature；（2）The suspension of formation is transferred in reactor, about 72 h are reacted under 180 °C；（3）Cooling down is to room temperature after reacting 72 h, scrubbed, drying to obtain LnOHCO3Ultrathin nanometer band.The present invention is obtained with hexagonal crystal phase, ultra-fine size, morphology controllable, the high-quality LnOHCO that is easily dispersed in non-polar solven by the step of solvent-thermal process method one3Ultrathin nanometer band, it is with low cost, it is easy to amplify synthesis, it is adaptable to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of rare earth hydroxycarbonate LnOHCO3The preparation method of ultrathin nanometer band, belongs to materials chemistry
Technical field.
Background technology
China is rare earth resources big country, and explored rare earth ore reserves accounts for more than half of world's gross reserves, and Rare Earth Mine
Thing great variety of goods, it is best in quality.Rare earth element has unique electronic structure, at aspects such as atom, molecule, the properties of compound
There is particularity different from transition elements and major element.Structure, property for rare earth element and association between the two
Property furtherd investigate in inorganic chemistry, materials chemistry so chemical field development be all significant.Rare earth element is unit
In plain periodic table in III B races atomic number 21 scandium（Sc）, 39 yttrium（Y）Lanthanum with 57（La）To 71 lutetium（Lu）Deng 17 units
The general name of element.Rare earth atoms structure is special, and internal layer 4f track unpaired electrons are more, atomic magnetic moment is high, electron energy level is abundant,
Can almost be reacted with all elements, form the rare earth compound with characteristics such as excellent magnetic, light, electricity, cores, be referred to as
Magical " new material treasure-house ".
Rare earth hydroxycarbonate is a kind of important rare earth compound, is increasingly paid close attention to by people.Rare earth hydroxyl carbon
Hydrochlorate is usually used to and prepares rare earth oxide, rare-earth oxide sulfate, while its own optics, magnetic property for having are also increasingly
The concern of people is received, optics is applied to and is shown and the field such as magnetic storage.
The content of the invention
It is an object of the invention to provide a kind of size is ultra-fine, morphology controllable, the LnOHCO that is easily dispersed in non-polar solven3It is super
The preparation method of thin nanobelt.
Implementation process of the present invention is as follows：
One kind prepares rare earth hydroxycarbonate LnOHCO3The method of ultrathin nanometer band, comprises the following steps：By acetic acid rare-earth salts
（Ln(Ac)3·6H2O）, urea（Co(NH2)2）It is dissolved in the mixed solution of oleyl amine and ethanol, stirring at room temperature forms suspension,
Transfer to 170-190 °C of reactions in closed reactor, after reaction terminates, scrubbed, drying to obtain LnOHCO3It is ultra-thin to receive
Rice band.
The LnOHCO for preparing3Ultrathin nanometer band has hexagonal crystal phase,a=12.06,b=12.06,c =
9.72,α=90.00,β=90.00,γ=90.00, nanometer bandwidth 5-10 nm, length 1-5 mm.
In above-mentioned preparation method, rare earth acetate is with the mol ratio of urea：1：80~120, the volume of oleyl amine and ethanol
Than for：1：2~4.
In above-mentioned preparation method, 170-190 °C of reaction 60-84h in closed reactor；Reaction temperature takes program control
Temperature, heating rate and rate of temperature fall are 1~3 °C/min.
Inventor have studied to form LnOHCO3The major influence factors of ultrathin nanometer band, mainly there is three aspects：（1）It is molten
The influence of agent.Solvent is to LnOHCO3The forming process of ultrathin nanometer band is very crucial, and the preparation of many inorganic nano materials is used
The mixed solvent of oleyl amine/oleic acid, inventor is had found in the presence of ethanol, for LnOHCO3The preparation of ultrathin nanometer band uses pure
Oleyl amine best results, change oleyl amine/oleic acid ratio or can not be obtained using oleic acid, hexylamine, lauryl amine, trioctylamine size surpass
Carefully, morphology controllable nano strip LnOHCO3.（2）Reaction temperature is also an important factor in order.170-190 °C of reactions can be obtained
To nano strip LnOHCO3, it is difficult to form nano strip LnOHCO higher than 190 °C or less than 170 °C3.（3）Reaction time
Influence.Reaction time is preferably in 60-84h.
Advantages of the present invention and significant progress are mainly reflected in：
By solvent-thermal process method, a step is obtained with hexagonal crystal phase, ultra-fine size, morphology controllable, is easily dispersed in the present invention
The high-quality LnOHCO of non-polar solven3Ultrathin nanometer band.Simultaneously synthesizing LnOHCO3Ultrathin nanometer band is shown in optics, magnetic
The fields such as storage suffer from special property with application.It is this to prepare high-quality LnOHCO3The method of ultrathin nanometer band can be with
The preparation of other metal hydroxy carbonate nano-functional materials is extended to, and it is with low cost, it is easy to amplifieroperation, it is adaptable to big rule
Mould industrialized production.
Brief description of the drawings
Fig. 1 is LnOHCO3（Ln=Eu, Gd, Ce, Dy, Sm）The X ray diffracting data of ultrathin nanometer band；
Fig. 2 is EuOHCO3Ultrathin nanometer band（a）Transmission electron microscope photo on a large scale,（b）Small range transmission electron microscope photo,（c）It is high
Differentiate photo,（d）Angle of elevation annular dark field scanning transmission electron microscope photo,（e）Stereoscan photograph.Illustration a is inverted EuOHCO3
Nanobelt forms gel in hexamethylene, and illustration b is EuOHCO3Scatter diagram of the nanobelt in hexamethylene, illustration c is single
EuOHCO3The SEAD figure of nanobelt；
Fig. 3 is GdOHCO3Ultrathin nanometer band（a）Transmission electron microscope photo on a large scale,（b）Small range transmission electron microscope photo,（c）It is high
Differentiate photo,（d）Angle of elevation annular dark field scanning transmission electron microscope photo,（e）Stereoscan photograph.Illustration a is inverted GdOHCO3
Nanobelt forms gel in hexamethylene, and illustration b is GdOHCO3Scatter diagram of the nanobelt in hexamethylene, illustration c is single
GdOHCO3The SEAD figure of nanobelt；
Fig. 4 is differential responses solvent ratios, the equally lower resulting GdOHCO of other reaction conditions3The transmission electron microscope of nanocrystal
Photo：（a）Pure oleyl amine,（b）Oleyl amine/oleic acid=1/1,（c）Oleyl amine/oleic acid=2/3,（d）Pure oleic acid；
Fig. 5 is different solvents, the equally lower resulting GdOHCO of other reaction conditions3The transmission electron microscope photo of nanocrystal：（a）
Hexylamine,（b）Lauryl amine,（c）Trioctylamine,（d）Oleyl amine；
Fig. 6 is different temperatures, the equally lower resulting GdOHCO of other reaction conditions3The transmission electron microscope photo of nanocrystal：（a）
90 DEG C,（b）120 DEG C,（c）150 DEG C,（d）180 DEG C,（e）210 ℃；
Fig. 7 is different time, the transmission electron microscope photo of the equally lower resulting nanocrystal of other reaction conditions：（a）12 h,
（b）24 h,（c）48 h,（d）72 h,（e）96 h；
Fig. 8 is LnOHCO3（Ln=Eu, Gd）Bulk transmission electron microscope photo：（a）EuOHCO3,（b）GdOHCO3；
Fig. 9 is LnOHCO3（Ln=Eu, EuOHCO3The transmission electron microscope photo of ultrathin nanometer band：Fig. 2-a；EuOHCO3Bulk it is saturating
Penetrate electromicroscopic photograph：Fig. 8-a）'s（a）EuOHCO3The ultraviolet-visible absorption spectroscopy of ultrathin nanometer band,（b）Fluorescence luminescence generated by light light
Spectrum：（c）Fluorescence lifetime spectrogram at 620 nm,（d）Obtained by being excited through 390 nm ultraviolet light beams under fluorescence microscope
EuOHCO3The luminescent image of ultrathin nanometer band；
Figure 10 is LnOHCO3（Ln=Gd, GdOHCO3The transmission electron microscope photo of ultrathin nanometer band：Fig. 3-a；GdOHCO3Bulk
Transmission electron microscope photo：Fig. 8-b；GdOHCO3The transmission electron microscope photo of nano-cluster：Fig. 5-c；GdOHCO3The transmission electron microscope of nanometer rods shines
Piece：Fig. 5-b）'s（a）Static magnetic moment experiment curv,（b）Magnetization curve；
Figure 11 is LnOHCO3（Ln=Sm, Ln=Ce, Ln=Dy）Ultrathin nanometer band.
Specific embodiment
The following is concrete application example of the invention, protection scope of the present invention is not limited in any way.All uses etc.
The technical scheme formed with conversion or equivalence replacement, all falls within rights protection scope of the present invention.
The LnOHCO of embodiment 13The preparation of ultrathin nanometer band（Ln=Eu, Gd, Dy, Ce or Sm）
By the Ln (AC) of 0.5 mmoL3·6H2Co (the NH of O, 50 mmoL2)2, it is dissolved in the mixing of 5 mL oleyl amines and 15 mL ethanol
In solution, suspension is formed after 30 min are stirred at room temperature.It is then transferred in the reactor of 25 mL, 180 °C of temperature programmed control
72 h of lower reaction, after the completion of reaction, reaction solution is cooled to room temperature, sequentially adds hexamethylene, ethanol, filters, washs, dries, and obtains
To LnOHCO3Ultrathin nanometer band.
Product is accredited as hexagonal crystal phase LnOHCO through powder x-ray diffraction3Ultrathin nanometer band（Fig. 1）；With transmission electron microscope, sweep
Retouch electron microscopic observation to the product be ultrathin nanometer band, width 5-10 nm, length 1-5 mm（Fig. 2, Ln=Eu, Fig. 3, Ln=
Gd）；LnOHCO3Ultrathin nanometer band morphology controllable, is attached to the electromicroscopic photograph under different experimental conditions（Accompanying drawing 4-7, Ln=Gd）；
LnOHCO is detected with XRF3Ultrathin nanometer band is presented in the case where 395 nm xenon lamps are excited at 595 nm and 615 nm
Obvious Eu3+Characteristic emission peak（Accompanying drawing 9, Ln=Eu）；By magnetic measurement LnOHCO3Ultrathin nanometer band has weaker anti-
Ferromagnetic behavior, static magnetic moment experiment curv display material magnetic moment keeps substantially constant, when temperature is less than 15 K, under magnetic moment value occurs
Drop trend, while the magnetization curve of material also shows weaker antiferromagnetic behavior（Accompanying drawing 10, Ln=Gd）.
Claims (6)
1. one kind prepares rare earth hydroxycarbonate LnOHCO3The method of ultrathin nanometer band, it is characterised in that comprise the following steps：Will
Acetic acid rare-earth salts, urea are dissolved in the mixed solution of oleyl amine and ethanol, and stirring at room temperature forms suspension, are transferred to closed anti-
Answer 170-190 °C of reactions in kettle, after reaction terminates, scrubbed, drying to obtain LnOHCO3Ultrathin nanometer band.
2. rare earth hydroxycarbonate LnOHCO according to claim 13The method of ultrathin nanometer band, it is characterised in that：Prepare
The LnOHCO for obtaining3Ultrathin nanometer band has hexagonal crystal phase,a=12.06,b=12.06,c =9.72,α=
90.00,β=90.00,γ= 90.00。
3. rare earth hydroxycarbonate LnOHCO according to claim 23The method of ultrathin nanometer band, it is characterised in that：Prepare
The LnOHCO for obtaining3Ultrathin nanometer bandwidth 5-10 nm, length 1-5 mm.
4. rare earth hydroxycarbonate LnOHCO according to claim 23The method of ultrathin nanometer band, it is characterised in that：Rare earth
Acetate is with the mol ratio of urea：1：80~120, oleyl amine is with the volume ratio of ethanol：1：2~4.
5. rare earth hydroxycarbonate LnOHCO according to claim 23The method of ultrathin nanometer band, it is characterised in that：Close
Close 170-190 °C of reaction 60-84h in reactor.
6. rare earth hydroxycarbonate LnOHCO according to claim 23The method of ultrathin nanometer band, it is characterised in that：Reaction
Temperature takes temperature programmed control, and heating rate and rate of temperature fall are 1~3 °C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109731147A (en) * | 2018-12-24 | 2019-05-10 | 西安交通大学 | Multi-functional PCS Hybrid nanofibers bio-medical method for producing elastomers and application |
Citations (2)
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|---|---|---|---|---|
| CN1369578A (en) * | 2001-02-13 | 2002-09-18 | 中国科学技术大学 | Alkaline rare earth-carbonate crystical film and its hydrothermal preparing process |
| CN105176516A (en) * | 2015-09-26 | 2015-12-23 | 哈尔滨工程大学 | Nuclear-shell photo-magnetic dual-mode imaging nanocrystalline and coprecipitation preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369578A (en) * | 2001-02-13 | 2002-09-18 | 中国科学技术大学 | Alkaline rare earth-carbonate crystical film and its hydrothermal preparing process |
| CN105176516A (en) * | 2015-09-26 | 2015-12-23 | 哈尔滨工程大学 | Nuclear-shell photo-magnetic dual-mode imaging nanocrystalline and coprecipitation preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHENYU XU等: "Controllable synthesis and optical properties of NdOHCO3 dodecahedral microcrystals", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109731147A (en) * | 2018-12-24 | 2019-05-10 | 西安交通大学 | Multi-functional PCS Hybrid nanofibers bio-medical method for producing elastomers and application |
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