CN109179508A - A kind of rare earth β-diketone complex3+Adulterate wolframic acid indium nano material and its preparation method and application - Google Patents
A kind of rare earth β-diketone complex3+Adulterate wolframic acid indium nano material and its preparation method and application Download PDFInfo
- Publication number
- CN109179508A CN109179508A CN201811381944.2A CN201811381944A CN109179508A CN 109179508 A CN109179508 A CN 109179508A CN 201811381944 A CN201811381944 A CN 201811381944A CN 109179508 A CN109179508 A CN 109179508A
- Authority
- CN
- China
- Prior art keywords
- nano material
- rare earth
- wolframic acid
- acid indium
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention provides a kind of rare earth dysprosium Dy3+Adulterate wolframic acid indium nano material and its preparation method and application, the nano material is in uniform nano bar-shape, and Dy3+The molar percentage of doping is 1% ~ 12%, and preparation method includes the following steps: taking InCl in proportion3、Na2WO4·2H2O and Dy (NO3)3·5H2O is dissolved in organic solvent, is added tetrabutylammonium bromide and is uniformly mixed, and uses the pH value of n-propylamine regulation system then isothermal reaction 8 ~ 20 hours post-process after reaction at 170 ~ 190 DEG C for 7.0 ~ 9.0 to obtain the final product；Wherein, InCl3With Dy (NO3)3·5H2The total amount and Na of O2WO4Molar ratio be 2:3.The preparation method of nano material of the present invention is simple, pattern favorable repeatability, and has good luminescent properties.
Description
Technical field
The invention belongs to wolframic acid indium technical field of nano material, and in particular to a kind of rare earth β-diketone complex3+Adulterate wolframic acid indium nanometer material
Material and its preparation method and application.
Background technique
Metal tungstates have potential application in every field, such as fluorescent powder, microwave, optical fiber, scintillator material, urge
Change and X-ray enhancing screen etc. [A. M. Kaczmarek, R. V. Deun,Chem. Soc. Rev., 2013, 42,
8835–8848; S. L. Gai, C. X. Li, P. P. Yang, J. Lin, Chem. Rev., 2014, 114,
2343−2389; Y. H. Zheng, J. T. Lin, Q. M. Wang, Photochem.Photobiol.Sci.,
2012, 11, 1567–1574; D. Chen, Z. Liu, S. X. Ouyang, J. H. Ye, J. Phys. Chem. C, 2011,115, 15778–15784; J. Zhang, Y. H. Wang, Z. Y. Zhai, G. B. Chen,Optical Mater., 2014, 38, 126–130].In recent years, since the unique luminescent properties of tungstates cause research
The concern of person, as a self-activation fluorophor, the inherent transmitting of metal tungstates fluorescent powder is about the width of 420 nm at center
Transmitting band, this is because O2-And WO4 2-Between charge migration transition caused by [T. Thongtem, S.
Kungwankunakorn, B. Kuntalue, A. Phuruangrat, S. Thongtem, J. Alloy Compd.,
2010, 506, 475–481; Z. Chen, Q. Gong, J. Zhu, Y.P. Yuan, L.W. Qian, X.F.
Qian, Mater. Res. Bull., 2009, 44, 45–50; C. Y. Li, X. D. Du, D.Yue, J. N.
Gao, Z. L. Wang, Mater. Lett., 2013,108, 257–260].In addition, tungstates is widely used in rare earth
The luminous host material of ion, to obtain new rare earth luminescent material [Maheshwary, B. P. Singh, J.
Singha, R. A. Singh, RSC Adv., 2014, 4, 32605–32621; Z. H. Ju, R. P. Wei, J.
X. Ma, C. R. Pang, W. S. Liu, J. Alloy Compd., 2010, 507, 133–136; Z. H. Ju,
R. P. Wei, X. P. Gao, W. S. Liu, C. R. Pang, Optical Mater., 2011, 33, 909–
913; J. S. Liao, B. Qiu, H. R. Wen, J. L. Chen, W. X. You, Mater. Res. Bull.,
2009, 44, 1863–1866; Maheshwary, B. P. Singh and R. A. Singh, New J. Chem.,
2015, 39, 4494–4507; B. Y. Xu, X. Cao, G. F. Wang, Y. Li, Y. P. Wang, J. M.
Su, Dalton Trans., 2014,43, 11493–11501].However, the preparation method of existing rare earth luminescent material exists
The disadvantages of yield is low, pattern is repeatable poor, especially with respect to rare earth dysprosium (Dy3+) doping wolframic acid indium nano luminescent material so far not
It appears in the newspapers.
Summary of the invention
The present invention tungstate material in the prior art there are aiming at the problem that, a kind of rare earth dysprosium Dy is provided3+Adulterate wolframic acid indium
Nano material and its preparation method and application, the material preparation method is simple, pattern favorable repeatability, and has good shine
Performance.
The present invention adopts the following technical scheme:
A kind of rare earth β-diketone complex3+Wolframic acid indium nano material is adulterated, the nano material is in uniform nano bar-shape, and with wolframic acid indium base
Dy in body3+And In3+Total moles meter, Dy3+The shared molar percentage of doping is 1% ~ 12%.
Preferably, the rare earth β-diketone complex3+The preparation method of wolframic acid indium nano material is adulterated the following steps are included: taking in proportion
InCl3、Na2WO4·2H2O and Dy (NO3)3·5H2O is dissolved in organic solvent, is added tetrabutylammonium bromide and is made template, is mixed
It closes uniformly, and uses the pH value of n-propylamine regulation system for 7.0 ~ 9.0, then isothermal reaction 8 ~ 20 hours at 170 ~ 190 DEG C,
After reaction, it post-processes to obtain the final product；
Wherein, InCl3 With Dy (NO3)3·5H2The total amount and Na of O2WO4·2H2The molar ratio of O is 2:3.
Preferably, the organic solvent is the mixed solvent of n-hexane and n,N-dimethylacetamide, and n-hexane and N,
The volume ratio of N- dimethyl acetamide is 1:6.
The rare earth β-diketone complex3+Adulterate application of the wolframic acid indium nano material in fluorescent material.
Beneficial effects of the present invention are as follows:
A kind of rare earth β-diketone complex is prepared in the present invention3+Nano bar-shape is presented in the wolframic acid indium nano material of doping, microscopic appearance, and
It is of uniform size, it is found by fluorometric investigation, under room temperature, which excites at 300 nm, 480
Emission peak is all obtained at nm and 570 nm, shows good photoluminescent property, can be used as fluorescent material use；In addition, this hair
Bright preparation method is simple, and mild condition, yield is higher, pattern favorable repeatability.
Detailed description of the invention
Fig. 1 is rare earth β-diketone complex3+The transmission electron microscope picture of the wolframic acid indium nano material of doping；
Fig. 2 is rare earth β-diketone complex3+The high-resolution-ration transmission electric-lens figure of the wolframic acid indium nano material of doping；
Fig. 3 is rare earth β-diketone complex3+The XRD spectra of the wolframic acid indium nano material of doping；
Fig. 4 is rare earth β-diketone complex3+The fluorescence spectra of the wolframic acid indium nano material of doping.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, with reference to the accompanying drawing and specifically
Embodiment is further illustrated technical solution of the present invention.
Embodiment 1
By InCl3(1.9 mmol), Na2WO4·2H2O(3.0 mmol) and Dy (NO3)3·5H2O(0.1 mmol) be dissolved in just oneself
The in the mixed solvent of alkane (1.0 mL) and n,N-dimethylacetamide (6.0 mL), and addition tetrabutylammonium bromide (TBAB, 1.0
Mmol), and it is transferred in 20 mL reaction kettles, tentatively stirs evenly, 20 μ L n-propylamines are then added dropwise, continue to stir evenly, adjusts
Save pH be 7.5 or so, then in 180 DEG C isothermal reaction 12 hours, cooled to room temperature, centrifuge separation take solid product and according to
After secondary use ethyl alcohol and hexamethylene wash repeatedly, it is drying to obtain rare earth β-diketone complex3+The wolframic acid indium nano material of doping.
Embodiment 2
It will be by InCl3(1.98 mmol), Na2WO4·2H2O(3.0 mmol) and Dy (NO3)3·5H2O(0.02 mmol) it is dissolved in
The in the mixed solvent of n-hexane (2.0 mL) and n,N-dimethylacetamide (4.0 mL), addition tetrabutylammonium bromide (TBAB,
1.0 mmol), and be transferred in 20 mL reaction kettles, it tentatively stirs evenly, 40 μ L n-propylamines is then added dropwise, it is equal to continue stirring
It is even, adjust pH be 8.5 or so, then in 170 DEG C isothermal reaction 16 hours, cooled to room temperature, centrifuge separation take solid to produce
Object and after successively being washed repeatedly with ethyl alcohol and hexamethylene, is drying to obtain rare earth β-diketone complex3+The wolframic acid indium nano material of doping.
Embodiment 3
It will be by InCl3(1.76 mmol), Na2WO4·2H2O(3.0 mmol) and Dy (NO3)3·5H2O(0.24 mmol) it is dissolved in
The in the mixed solvent of n-hexane (2.0 mL) and n,N-dimethylacetamide (4.0 mL), addition tetrabutylammonium bromide (TBAB,
1.0 mmol), and be transferred in 20 mL reaction kettles, it tentatively stirs evenly, 40 μ L n-propylamines is then added dropwise, it is equal to continue stirring
It is even, adjust pH be 8.5 or so, then in 170 DEG C isothermal reaction 20 hours, cooled to room temperature, centrifuge separation take solid to produce
Object and after successively being washed repeatedly with ethyl alcohol and hexamethylene, is drying to obtain rare earth β-diketone complex3+The wolframic acid indium nano material of doping.
Rare earth β-diketone complex prepared by Example 13+The wolframic acid indium nano material of doping carries out XRD test (Rigaku Ultima
III diffractometer, CuKa (λ=1.5418), operating voltage 40 kV and 40 mA) and transmission electron microscope characterization (FEI TECNAI
G2), while the emission spectrum of the nano material and excitation spectrum use Edinburgh Instruments FLS980 fluorescence
Meter, there are two light source, 450 W light sources and xenon flash lamps for luminoscope outfit.
Transmission electron microscope characterization is shown in Fig. 1, Fig. 2, it will be seen from figure 1 that rare earth β-diketone complex prepared by embodiment 13+The wolframic acid of doping
Indium nano material is in uniform nanometer rods pattern, and diameter is about 16 nm, and length is about 104 nm, as can be seen from Figure 2, rare earth β-diketone complex3+It mixes
Miscellaneous wolframic acid indium nano material shows clearly lattice fringe, shows that nanometer rods are crystalline texture；XRD diagram is shown in Fig. 3, can see
Out, In2(WO4)3And In2(WO4)3:Dy3+XRD peak position it is consistent, the In with orthorhombic phase2W3O12Standard PDF card (PDF#49-
0337) it is consistent, shows Dy3+After doping, In2(WO4)3Lattice structure remain unchanged.
In2(WO4)3:Dy3+Fig. 4 is shown in the photoluminescent property test of nanometer rods solid sample, under room temperature, swashs at 300 nm
Hair, all obtains emission peak at 480 nm and 570 nm, can be used as fluorescent material use.
It should be noted last that: technical solution of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or locally replace that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (4)
1. a kind of rare earth β-diketone complex3+Adulterate wolframic acid indium nano material, which is characterized in that the nano material is in uniform nano bar-shape,
And with Dy in wolframic acid indium matrix3+And In3+Total moles meter, Dy3+The shared molar percentage of doping is 1% ~ 12%.
2. rare earth β-diketone complex described in claim 13+Adulterate the preparation method of wolframic acid indium nano material, which is characterized in that including following
Step: InCl is taken in proportion3、Na2WO4·2H2O and Dy (NO3)3·5H2O is dissolved in organic solvent, adds tetrabutyl phosphonium bromide
Ammonium is uniformly mixed, and uses the pH value of n-propylamine regulation system for 7.0 ~ 9.0, the then isothermal reaction 8 ~ 20 at 170 ~ 190 DEG C
Hour, after reaction, post-process to obtain the final product；
Wherein, InCl3 With Dy (NO3)3·5H2The integral molar quantity and Na of O2WO4·2H2The molar ratio of O mole is 2:3.
3. rare earth β-diketone complex according to claim 23+Adulterate the preparation method of wolframic acid indium nano material, which is characterized in that described
Organic solvent is the mixed solvent of n-hexane and n,N-dimethylacetamide, and the volume of n-hexane and n,N-dimethylacetamide
Than for 1:6.
4. rare earth β-diketone complex described in claim 13+Adulterate application of the wolframic acid indium nano material in fluorescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811381944.2A CN109179508B (en) | 2018-11-20 | 2018-11-20 | Rare earth Dy3+Indium tungstate doped nano material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811381944.2A CN109179508B (en) | 2018-11-20 | 2018-11-20 | Rare earth Dy3+Indium tungstate doped nano material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109179508A true CN109179508A (en) | 2019-01-11 |
| CN109179508B CN109179508B (en) | 2020-10-02 |
Family
ID=64940157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811381944.2A Expired - Fee Related CN109179508B (en) | 2018-11-20 | 2018-11-20 | Rare earth Dy3+Indium tungstate doped nano material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109179508B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935360A (en) * | 2012-11-14 | 2013-02-20 | 陕西科技大学 | Method for preparing ZnWO4 nanorod photocatalysis material |
| CN105679546A (en) * | 2016-01-18 | 2016-06-15 | 黑龙江大学 | InWO4:Eu<3+>/TiO2 composite photo anode and preparation method thereof |
| CN106497487A (en) * | 2016-10-28 | 2017-03-15 | 安徽工业大学 | A kind of molybdic acid indium nanometer rods high-temperature seal adhesive |
-
2018
- 2018-11-20 CN CN201811381944.2A patent/CN109179508B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935360A (en) * | 2012-11-14 | 2013-02-20 | 陕西科技大学 | Method for preparing ZnWO4 nanorod photocatalysis material |
| CN105679546A (en) * | 2016-01-18 | 2016-06-15 | 黑龙江大学 | InWO4:Eu<3+>/TiO2 composite photo anode and preparation method thereof |
| CN106497487A (en) * | 2016-10-28 | 2017-03-15 | 安徽工业大学 | A kind of molybdic acid indium nanometer rods high-temperature seal adhesive |
Non-Patent Citations (1)
| Title |
|---|
| ANUKORN PHURUANGRAT等: "Influence of Dy dopant on photocatalytic properties of Dy-doped ZnWO4 nanorods", 《MATERIALS LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109179508B (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tian et al. | Synthesis and luminescent properties of spindle-like CaWO4: Sm3+ phosphors | |
| Raju et al. | Luminescence properties of Dy3+: GdAlO3 nanopowder phosphors | |
| CN106433634B (en) | A kind of preparation method of monodisperse pulmbous sulfide quantum dot | |
| Sohal et al. | Effect of Tb3+ concentration on the optical and vibrational properties of YBO3 tri-doped with Eu3+, Ce3+, and Tb3+ | |
| Liang et al. | A user-friendly method for synthesizing high-quality NaYF4: Yb, Er (Tm) nanocrystals in liquid paraffin | |
| Ramteke et al. | Eu3+ and Dy3+-activated LaAlO3 phosphor for solid-state lighting | |
| Shi et al. | Effect of W6+ dopant on the morphology and luminescence properties of NaLa (MoO4) 2: Eu3+ phosphors | |
| Liu et al. | Direct low-temperature synthesis of ultralong persistent luminescence nanobelts based on a biphasic solution-chemical reaction | |
| Sun et al. | Synthesis, deep red emission and warm WLED applications of K2SiF6: Mn4+ phosphors | |
| Tian et al. | Synthesis and characterization of novel red emitting nanocrystal Gd6WO12: Eu3+ phosphors | |
| Yi et al. | Tunable multicolor upconversion luminescence and paramagnetic property of the lanthanide doped fluorescent/magnetic bi-function NaYbF4 microtubes | |
| CN103275715B (en) | Preparation method of rare earth molybdate matrix red nanophosphor | |
| Wu et al. | Controllable preparation and fluorescence property of spherical nano-phosphor YPO4: Eu3+ | |
| Gong et al. | Preparation and photoluminescence properties of ZrO2 nanotube array-supported Eu3+ doped ZrO2 composite films | |
| Lei et al. | Lanthanide-doped bismuth-based fluoride nanoparticles: controlled synthesis and ratiometric temperature sensing | |
| Zhang et al. | Synthesis and the temperature-dependent luminescent properties of SrWO4: Eu3+ ultralong nanowire phosphors | |
| Mu et al. | Synthesis and luminescent properties of Rare Earth (Eu2+, Tb3+) doped Ba3 (PO4) 2 nanowires by chemical precipitation in nanochannels | |
| JP5655136B2 (en) | Fluorescent material for field emission and preparation method thereof | |
| CN109179508A (en) | A kind of rare earth β-diketone complex3+Adulterate wolframic acid indium nano material and its preparation method and application | |
| Gui et al. | Hydrothermally synthesized β-NaGdF4: Eu3+@ β-NaGdF4: Ce3+, Dy3+ phosphors with multicolor luminescence properties via dual-channel excitation and energy migration procedure | |
| Han et al. | Self-assembled synthesis and photoluminescence properties of uniform Dy2O3 microspheres and tripod-like structures | |
| CN108531180B (en) | Fluorescence adjustable core-shell nanocrystal and preparation method thereof | |
| Zhu et al. | Hydrothermal synthesis and photoluminescent properties of YV 1− x P x O 4: Eu 3+(x= 0–1.0) nanophosphors | |
| Han et al. | CTAB-assisted precipitation synthesis and photoluminescence properties of olive-like YVO4: Eu nanocrystallites | |
| Lei et al. | Improvement of the luminescent intensity of Yb/Er: CaF2 nanocrystals by combining Na+-doping and active-core/active-shell structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201002 Termination date: 20211120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |