CN108690605B - Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof - Google Patents
Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof Download PDFInfo
- Publication number
- CN108690605B CN108690605B CN201810686236.3A CN201810686236A CN108690605B CN 108690605 B CN108690605 B CN 108690605B CN 201810686236 A CN201810686236 A CN 201810686236A CN 108690605 B CN108690605 B CN 108690605B
- Authority
- CN
- China
- Prior art keywords
- tellurium tungstate
- tellurium
- erbium
- functionalized
- tungstate material
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 104
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 89
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 14
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000004020 luminiscence type Methods 0.000 claims abstract description 22
- 229910004273 TeO3 Inorganic materials 0.000 claims abstract description 11
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims abstract description 9
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910020350 Na2WO4 Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 description 25
- 229910052761 rare earth metal Inorganic materials 0.000 description 18
- -1 molecular sensors Substances 0.000 description 16
- 125000004430 oxygen atom Chemical group O* 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000006399 behavior Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- NKWCGTOZTHZDHB-UHFFFAOYSA-N 1h-imidazol-1-ium-4-carboxylate Chemical compound OC(=O)C1=CNC=N1 NKWCGTOZTHZDHB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000370001 Hantavirus Liu Species 0.000 description 1
- 229910003177 MnII Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BFPJYWDBBLZXOM-UHFFFAOYSA-L potassium tellurite Chemical compound [K+].[K+].[O-][Te]([O-])=O BFPJYWDBBLZXOM-UHFFFAOYSA-L 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 150000003497 tellurium Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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
Images
Classifications
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/183—Metal complexes of the refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta or W
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a dimethyl tin functionalized tellurium tungstate material which contains polyacid mixed building blocks and is embedded with erbium, and the chemical formula of the tellurium tungstate material is as follows: [ H ]2N(CH3)2]8H6[Er2(OH)(B‑α‑TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O, belonging to the monoclinic system,P2/cspace group, cell parameter ofa=17.923(3)Å，b=17.882(3)Å，c=29.463(4)Å，α=90.00º，β=122.22º，γ=90.00º,V=7989(2)Å3,Z=2,R 1=0.0812,wR 2=0.1635 the dimethyl tin is functionalized and comprises { B- α -TeW7O28And { W }5O18The synthesis of the erbium-embedded tellurium tungstate material with the mixed building blocks adopts a one-step assembly strategy and utilizes a simple raw material Na2WO4·2H2O、Sn(CH3)2Cl2、Er(NO3)3·6H2O, dimethylamine hydrochloride and K2TeO3Obtained by reaction under the condition of aqueous solution. The invention researches the photoluminescence properties of the material in a visible region and a near infrared region, prepares Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions, researches the photoluminescence properties of the material in the visible region and the near infrared region, and observes for the first timeAnd (3) the up-conversion luminescence phenomenon of Er/Yb =0.06:0.94 co-doped tellurium tungstate material.
Description
Technical Field
The invention belongs to the technical field of preparation of polyoxometallate materials, and particularly relates to a functional dimethyltin material containing { B- α -TeW7O28And { W }5O18Preparation method of erbium-embedded tellurium tungstate material and application in fluorescent material field.
Background
In recent years, with the rapid development of science and technology, scientists have studied more on the application of fluorescence mainly in the aspects of fluorescent probes, molecular sensors, substance detection, luminescent devices, rare earth doped luminescent materials, metal-organic framework luminescent materials and the like, and design and preparation of fluorescent materials with excellent performance attract great attention (see y.l. Zhang, x.h. Liu, y.b. Lang,et al. J. Mater. Chem. C2015,3, 2045-2053). As is well known, polyoxometallates (simply referred to as polyacids) are formed by an oxygen atom and an early transition metal in the highest valence state6Octahedron and tetrahedron { XO formed by low valence metal ion, non-metal ion and oxygen4} or triangular pyramid { XO3And connecting the metal anion clusters in a mode of sharing edges, angles and planes to form the multi-metal anion clusters with different structures. Because polyoxometallate has the characteristics of rich structural composition, nano-scale size, good thermal stability, excellent electrochemical performance, high protonic acidity and the like, the polyoxometallate has wide application prospects in catalysis, medicine, material science and the like (see L. Huang, S.S. Wang, J. W.ZHao,et al.J. Am. Chem. Soc.2014,136, 7637-7642). Meanwhile, the rare earth element is a general name of sixteen kinds of metal elements including lanthanide elements, yttrium and the like, and has lanthanide contraction characteristics, particularly lanthanide contraction of 14 elements from La to Lu is very obvious, so that when a rare earth derivative of a polytungstate is prepared, differences of rare earth ions tend to form derivatives with various structures. Moreover, 4f layer electron orbitals in the rare earth ions are shielded by fully filled 5s and 5p orbitals, and the fluorescent material has good fluorescenceThe rare earth ions have high spin property due to a large amount of unpaired 4f electrons, so the rare earth ions have wider application value in the aspects of optical and magnetic properties and the like (see K. Binnemans).Chem. Rev. 2009,109,4283–4374）。
In recent years, scientists have been working on polyoxometallate materials with tellurium tungstate as building blocks. Transition metal substituted tellurium tungstates have been reported, for example [ (Mn)II(H2O)3)2(MnII(H2O)2)2(TeW9O33)2]8−,[Fe4(H2O)10(β-TeW9O33)2]4–, [{RuIV 4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]−, [H10Ag18Cl(Te3W38O134)2]29−, [Pd6Te19W42O190]40−And [ { Co (L) ((H))2O)}2(WO2)2(TeW9O33)2]10−(L = 1H-imidazole-4-carboxylate, 1H-imidazole-4-carboxylic acid) (see M. B ö sing, A. N ö H, I. lose,et al. J. Am. Chem. Soc.1998,120, 7252–7259; U. Kortz, M. G. Savelieff, B. S.Bassil,et al.Inorg. Chem.2002,41, 783–789; I. V. Kalinina, N. V. Izarova,U. Kortz,et al. Inorg. Chem.2012,51, 7442−7444; C. H. Zhan, J. M. Cameron,G. J. Gao,et al. Angew. Chem. Int. Ed.2014,53, 10362–10366; J. M. Cameron,J. Gao, D. L. Long,et al.Inorg. Chem. Front.2014,1, 178−185; B. Artetxe,S. Reinoso, L. S. Felices,et al.Inorg. Chem. 2015,54, 241-252). However, reports on rare earth substituted tellurium tungstate materials are rare, such as two examples of polynuclear cerium substituted tellurium tungstate materials [ { (TeO) reported in the Suzhongzi problem group3)W10O34}8{Ce8(H2O)20}(WO2)4(W4O12)]48-And [ Ce ]10Te8W88O298(OH)12(H2O)40]18-(see W.C. Chen, H.L. Li, X.L. Wang,et al. Chem. Eur. J. 2013,19, 11007–11015; W. C. Chen, C. Qin, X. L. Wang,et al.Dalton Trans.2015,4411290-11293.) and our topic group reported a series of rare earth substituted tellurium tungstate materials [ RE ] modified by pyridine carboxylic acid2(H2O)4(pica)2W2O5][(RE(H2O)W2(Hpica)2O4)(B-β-TeW8O30H2)2]24-(RE = LaIII, CeIII,NdIII, SmIII, EuIIIHpica = 2-picolinic acid) (see Q. Han, Y. Wen, J.C. Liu,et al.Inorg. Chem.2017,56, 13228-13240). At present, researches on luminescence and up-conversion luminescence of rare earth substituted tellurium tungstate materials are very rare, so that designing rare earth substituted tellurium tungstate materials and realizing fluorescence luminescence detection are necessary, but reports on rare earth doped tellurium tungstate materials with up-conversion luminescence behaviors are not seen at present. In the research field, the main problem is that the tellurium tungstate material has poor reactivity in a reaction system, so that rare earth ions in the reaction process are easy to generate precipitates and crystals cannot be obtained. Therefore, it is a very challenging and meaningful research effort to prepare organic tin functionalized rare earth substituted tellurium tungstate and rare earth doped tellurium tungstate materials and to explore their properties in terms of luminescence.
Disclosure of Invention
The invention aims to provide a functional dimethyltin alloy which contains { B- α -TeW7O28And { W }5O18And (3) embedding erbium into a tellurium tungstate material (1-Er), doping Er/Yb with tellurium tungstate materials (1-Er/Yb) with different proportions, and a preparation method and application thereof in the field of luminescence.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a dimethyl tin functionalized and polyacid-containing mixed building block erbium-embedded tellurium tungstate material specifically comprises the following steps:
mixing Na2WO4·2H2O, dimethylamine hydrochloride, K2TeO3And Sn (CH)3)2Cl2Dissolving in distilled water, adjusting pH to 6.0-6.5, and adding Er (NO)3)3·6H2O or Er (NO)3)3·6H2O and Yb (NO)3)3·6H2And (3) mixing O, adjusting the pH value to 6.0-6.5 again, stirring and dissolving, filtering out impurities, standing the filtrate at room temperature for volatilization, and separating out pink blocky solid which is the tellurium tungstate material.
Specifically, the Na2WO4·2H2O, dimethylamine hydrochloride, K2TeO3、Er(NO3)3∙6H2O、Sn(CH3)2Cl2And distilled water are preferably in a molar ratio of 10.6 to 16.7: 24.4: 0.78: 1.14-3.82: 1.00: 1660-1670; er (NO)3)3·6H2O and Yb (NO)3)3·6H2The mass ratio of O is preferably controlled to be 0.96: 0.04-0.02: within the range of 0.98.
The invention also discloses the dimethyl tin functionalized tellurium tungstate material which is prepared by the preparation method and contains polyacid mixed building blocks erbium embedded. During the preparation process, only Er (NO) is added3)3·6H2When O is obtained, the chemical formula of the obtained tellurium tungstate material is as follows: [ H ]2N(CH3)2]8H6[Er2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O (i.e., 1-Er); when the added raw material is Er (NO)3)3·6H2O and Yb (NO)3)3·6H2In the case of O mixture, Er (NO) is controlled3)3·6H2O and Yb (NO)3)3·6H2The mass ratio of O can obtain Er/Yb co-doped tellurium tungstate materials (1-Er/Yb) with different ratios.
The invention also provides application of the tellurium tungstate material which is functionalized by dimethyl tin and contains polyacid mixed building blocks and embedded with erbium in the field of luminescence.
Further, the application of the tellurium tungstate material which is functionalized by dimethyl tin and contains polyacid mixed building blocks and is embedded into erbium in the field of luminescence, and particularly the tellurium tungstate material can be used as a luminescent material.
Further, the application of the above dimethyl tin functionalized tellurium tungstate material containing polyacid mixed building blocks embedded into tellurium tungstate material in the field of luminescence, in particular to the application of the tellurium tungstate material as an up-conversion luminescent material, especially the application of Er/Yb codoped tellurium tungstate material (1-Er/Yb) with different proportions in the aspects of luminescent material and up-conversion luminescent material.
In the invention, a one-step self-assembly strategy is adopted, sodium tungstate, dimethylamine hydrochloride, potassium tellurite, dimethyl tin dichloride and erbium nitrate in a certain molar ratio are reacted under the condition of aqueous solution to obtain an organic tin functionalized organic tin containing { B- α -TeW }7O28And { W }5O18And (4) mixing to form the erbium-embedded tellurium tungstate material. In the reaction, a one-step self-assembly strategy is adopted, and simple reaction raw materials are utilized to prepare the organotin functionalized erbium-embedded tellurium tungstate material with a unique structure. The synthesis idea is as follows:
(
) Te having lone pair electron stereochemical effectIVAtoms can prevent the formation of saturated tellurium tungstate fragments, and at the same time, TeIVAtoms have larger ionic radius, which is beneficial to forming high-vacancy tellurium tungstate fragments;
(
) The rare earth ions have high coordination number and strong oxygen affinity, show extremely strong bonding capability to oxygen atoms on the surface of the tellurium tungstate, and are connected throughThe tellurium tungstate fragments form novel structures. In addition, the rare earth ions can also be clustered by self-aggregation to enhance the stability of the whole framework through bonding;
() The reaction system of the excess tungstate provides possibility for constructing isopoly tungsten and heteropoly tungsten anion fragments;
(iv) the organic tin shows active chemical property in a tellurium tungstate system and is easy to be embedded into the defect segment of the tellurium tungstate.
Compared with the prior art, the invention has the following advantages:
1) the invention provides a functional dimethyl tin containing { B- α -TeW7O28And { W }5O18The crystal structure of the erbium-embedded tellurium tungstate material constructed by mixing can be accurately determined by X-ray single crystal diffraction;
2) the invention provides a functional dimethyl tin containing { B- α -TeW7O28And { W }5O18The Er-embedded tellurium tungstate material of the mixed building block and the Er/Yb co-doped tellurium tungstate material with different proportions are obtained by adopting a one-step self-assembly method, so that the operation is convenient and easy to implement, and the potential application prospect is realized;
3) the invention provides a functional dimethyl tin containing { B- α -TeW7O28And { W }5O18The Er/Yb co-doped tellurium tungstate material with the up-conversion luminescence behavior is discovered for the first time;
4) the invention provides a functional dimethyl tin containing { B- α -TeW7O28And { W }5O18And the erbium is embedded into the tellurium tungstate material to provide experimental basis and theoretical reference for discovering and preparing other organic tin functionalized rare earth substituted polyoxometallate luminescent materials.
Drawings
In FIG. 1, (a) dimethyl tin is functionalized and comprises { B- α -TeW }7O28And { W }5O18A molecular structure unit diagram of a mixed building block erbium embedded tellurium tungstate material, (b) a polyanion fragment [ Er (OH) (TeW)7O28)ErSn2(CH3)4(W5O18)]7-Structure diagram, (c) Er13+、Sn14+And Sn24+Coordination environment of ions, (d) Er23+And Er2A3+A tetragonal antiprism coordination configuration of ions, (e-f) a three-dimensional supramolecular packing diagram and simplified model diagram along the c-axis, (g) a dimethyltin functionalized polymer comprising { B- α -TeW }7O28And { W }5O18Mixed building block erbium embedded tellurium tungstate material variable temperature X-ray powder diagram, (h) dimethyl tin functionalized containing { B- α -TeW }7O28And { W }5O18A temperature-variable infrared spectrogram of a mixed building block erbium-embedded tellurium tungstate material (i) a functional mixture of dimethyl tin and (ii) B- α -TeW7O28And { W }5O18Embedding erbium into a tellurium tungstate material variable-temperature fluorescence emission spectrogram through mixed construction;
FIG. 2 is a functional dimethyltin compound comprising { B- α -TeW }7O28And { W }5O18An infrared spectrogram of a mixed building block of erbium-embedded tellurium tungstate material, showing thereinν(W–Ot)，ν(W–Ob)，ν(W–Oc) Andν(Te–Oa) The characteristic of (1) a telescopic vibration absorption band;
FIG. 3 is a functional dimethyltin compound comprising { B- α -TeW }7O28And { W }5O18The thermal weight loss curve of the erbium-embedded tellurium tungstate material constructed by mixing shows that the weight loss process mainly belongs to crystal water, coordinated water, dimethylamine and H+Loss of ions and loss of dimethyl tin;
in FIG. 4, (a) the solid-state visible fluorescence emission spectra of Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions under 381 nm excitation; (b) at 558 nm, the intensity change diagram of the strongest fluorescence emission peak of Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions; (c) under the excitation of 381 nm, Er/Yb codoped with tellurium tungstate material 1-Er/Yb in different proportions emits a solid-state near-infrared fluorescence spectrum; (d) a change graph of the strongest fluorescence emission peak intensity of Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions at 1532 nm;
in FIG. 5, (a) the visible region fluorescence lifetime decay curves of different ratios of Er/Yb co-doped tellurium tungstate material 1-Er/Yb under excitation at 381 nm and emission at 556 nm; (b) the average life value of Er/Yb codoped tellurium tungstate material 1-Er/Yb in different proportions in a visible region; (c) under the excitation condition of 381 nm and the emission condition of 1531 nm, Er/Yb codoped with tellurium tungstate material 1-Er/Yb with different proportions has a near infrared region fluorescence lifetime attenuation curve; (d) the Er/Yb codoped tellurium tungstate material has the average life value of 1-Er/Yb in different proportions in the near infrared region;
FIG. 6 is a graph of (a) upconversion fluorescence emission spectra of Er/Yb co-doped tellurium tungstate materials 1-Er/Yb with different ratios under 980 nm light excitation; (b) a graph of the variation of the strongest fluorescence emission peak intensity of Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions and located at 531 nm along with the Er/Yb doping proportion; the inset in b shows that the Er/Yb doping ratio mass ratio is between 0.96: 0.04-0.16: 0.84, and the intensity of the corresponding emission peak.
Detailed description of the invention
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1:
a functional dimethyltin alloy comprising { B- α -TeW }7O28And { W }5O18The erbium-embedded tellurium tungstate material is obtained by a one-step self-assembly method by utilizing simple raw materials, and the preparation method specifically comprises the following steps:
under the condition of stirring, adding Na2WO4·2H2O (3.500 g, 10.612 mmol)、K2TeO3(0.200 g,0.7839 mmol)、Sn(CH3)2Cl2(0.220 g, 1.001 mmol) and dimethylamine hydrochloride (2.000 g, 24.445mmol) were added to 30 mL of distilled water followed by 6 mol ∙ L–1Adjusting the pH of the reaction system to 6.50, continuously stirring for about 10min to dissolve completely, and addingEr (NO)3)3·6H2O (0.500 g, 1.143 mmol) in an amount of 0.5 mol ∙ L–1The pH of the reaction system was adjusted to 6.50 again with NaOH, and after stirring was continued for about 30 min, impurities were filtered off by filtration. And standing the filtrate at room temperature for volatilization, and precipitating after about three weeks to obtain a pink blocky solid, namely the target material 1-Er. Yield: 0.91 g, yield: 28.52% (in K)2TeO3Calculation). The chemical formula of the target material 1-Er is as follows: [ H ]2N(CH3)2]8H6[Er2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O。
Under the same conditions, Er (NO) is controlled3)3·6H2O and Yb (NO)3)3·6H2The mass ratio of O is used for preparing Er/Yb co-doped tellurium tungstate materials (1-Er/Yb) with different proportions, and the preparation method is different from the preparation method of the target material 1-Er in that: with Er (NO)3)3·6H2O and Yb (NO)3)3·6H2Replacement of Er (NO) by a mixture of O3)3·6H2O, i.e. retaining Er (NO)3)3·6H2O and Yb (NO)3)3·6H2The total mass of O is 0.500 g, Er (NO) is controlled3)3·6H2O and Yb (NO)3)3·6H2The mass ratio of O is 0.02:0.98, 0.06:0.94, 0.16:0.84, 0.20:0.80, 0.40:0.60, 0.60:0.40 and 0.96:0.04, respectively.
Example 2:
a functional dimethyltin alloy comprising { B- α -TeW }7O28And { W }5O18The erbium-embedded tellurium tungstate material with the mixed building blocks is obtained by a one-step self-assembly method by utilizing simple raw materials, and the preparation method specifically comprises the following steps:
under the condition of stirring, adding Na2WO4·2H2O (5.500 g, 16.676 mmol)、K2TeO3(0.200 g,0.7839 mmol)、Sn(CH3)2Cl2(0.220 g, 1001 mmol) and dimethylamine hydrochloride (2.000 g, 24.445mmol) were added to 30 mL of distilled water followed by 6 mol ∙ L–1Adjusting the pH of the reaction system to 6.50, continuously stirring for about 10min to dissolve completely, and then adding Er (NO)3)3·6H2O (0.500 g, 1.143 mmol) in an amount of 0.5 mol ∙ L–1The pH of the reaction system was adjusted to 6.50 again with NaOH, and after stirring was continued for about 30 min, impurities were filtered off by filtration. And standing the filtrate at room temperature for volatilization, and precipitating after about three weeks to obtain a pink blocky solid, namely the target material 1-Er. Yield: 1.04 g, yield: 32.60% (in K)2TeO3Calculation). The chemical formula of the target material 1-Er is as follows: [ H ]2N(CH3)2]8H6[Er2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O。
Example 3:
a functional dimethyltin alloy comprising { B- α -TeW }7O28And { W }5O18The erbium-embedded tellurium tungstate material with the mixed building blocks is obtained by a one-step self-assembly method by utilizing simple raw materials, and the preparation method specifically comprises the following steps:
under the condition of stirring, adding Na2WO4·2H2O (3.500 g, 10.612 mmol)、K2TeO3(0.200 g,0.7839 mmol)、Sn(CH3)2Cl2(0.220 g, 1.001 mmol) and dimethylamine hydrochloride (2.000 g, 24.445mmol) were added to 30 mL of distilled water followed by 6 mol ∙ L–1Adjusting the pH of the reaction system to 6.50, continuously stirring for about 10min to dissolve completely, and then adding Er (NO)3)3·6H2O (1.670 g, 3.810 mmol) in an amount of 0.5 mol ∙ L–1The pH of the reaction system was adjusted to 6.50 again with NaOH, and after stirring was continued for about 30 min, impurities were filtered off by filtration. And standing the filtrate at room temperature for volatilization, and precipitating after about three weeks to obtain a pink blocky solid, namely the target material 1-Er. Yield: 0.85 g, yield: 26.64% (in K)2TeO3Calculation). The chemical formula of the target material 1-Er is：[H2N(CH3)2]8H6[Er2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O。
The invention adopts an X-ray single crystal diffraction technology to functionalize the dimethyltin and comprises { B- α -TeW }7O28And { W }5O18The crystal structure of the erbium-embedded tellurium tungstate material of the mixed building block is determined and characterized, and the unit cell parameters are as follows:
the dimethyltin is functionalized and comprises { B- α -TeW }7O28And { W }5O18Mix and build the tellurium tungstate material (1-Er) H embedded in erbium2N(CH3)2]8H6[Er2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O belongs to the monoclinic system and has a space group ofP2/cParameter of unit cella= 17.923(3) Å,b= 17.882(3) Å,c= 29.463(4) Å,a=90°,β= 122.20(7)°,g= 90°,V= 7989(2) Å3,Z= 2,R 1= 0.08,wR 2= 0.1635[I>2σ(I)]The dimethyltin is functionalized and comprises { B- α -TeW }7O28And { W }5O18The structure of erbium-embedded tellurium tungstate material (1-Er) of the mixed building block is described as follows: the molecular structure of the nano-particle comprises a tetra polyanion [ Er (OH) (TeW)7O28)ErSn2(CH3)4(W5O18)]2 14–(FIG. 1a), eight [ H ]2N(CH3)2]+Ion, six H+Ions and eighteen crystalline water molecules. Tetrapolyanionic [ Er (OH) (TeW)7O28)ErSn2(CH3)4(W5O18)]2 14–Is composed of two symmetric dimeric anionic units [ Er (OH) (TeW)7O28)ErSn2(CH3)4(W5O18)]7–(FIG. 1b) is bonded via an oxygen atom. Two crystallographically independent Er exist in the compound3+Ions. Er13+The ion assumes the configuration of an eight-coordinated double-capped triangular prism (FIG. 1c) in which four of the eight coordinated oxygen atoms are terminal oxygen atoms (O34, O7, O1, O8) and one is derived from [ W5O18]6−Unit mu2An O atom (O24) having a bond length in the range of [ Er-O: 2.264(17) -2.654 (16) Å]The three oxygen atoms (O4, O2, O9) are from [ TeW ]7O28]10–Building blocks with bond length range of [ Er-O: 2.263(16) -2.546 (16) Å]. In Er13+In the ion's double-capped triangular prism configuration, the O24 and O9 atoms occupy two capped positions, respectively, and the remaining six oxygen atoms form the six vertices of a triangular prism. In Er23+In the tetragonal antiprism configuration of the ion (FIG. 1d), two μ2O atoms (O3, O3A) simultaneously bonded to Er23+And Er2A3+Ions with a bond length in the range of Er 2-O2.2652-2.5464 Å, three oxygen atoms (O14, O17, O19) from another [ TeW ]7O28]10−Building units with bond length in the range of Er-O2.2652-2.4939 Å and in Er13+Two crystallographically independent Sn at two ends of the ion4+The ions all adopt a five-coordinate triangular bipyramid geometric configuration. Sn14+The triangular bipyramid geometric configuration of the ion consists of two mu3-O atom (O2, O8), one μ2-O atom (O20) and two carbon atoms (C1, C2), the bond length of Sn 1-O being in the range of 2.011(16) -2.239 (17) Å, Sn24+The triangular bipyramid geometric configuration of the ion consists of two mu3-O atom (O1, O4), one μ2-O atoms (O36) and two carbon atoms (C3, C4), the Sn 2-O bond length ranging from 2.0711(16) -2.226 (17) Å it is worth noting that from a three-dimensional stacking diagram along the a-axis direction, the compound tetrapolyanion exhibits an-ABAB-stacking pattern along the a-direction, the distance of two adjacent tetrapolyanions along the a-direction is 17.923 Å, along the b-direction is 17.882 Å, and along the C-direction is 29.463 Å (fig. 1 e). from a three-dimensional stacking diagram along the C-direction, two adjacent layers adopt different stacking patterns, exhibiting two layers mutually different stacking patternsStaggered arrangement pattern (fig. 1 f).
More interestingly, the thermal decomposition process of the target material 1-Er is intensively studied by means of testing means such as variable temperature X-ray powder diffraction, variable temperature infrared and variable temperature fluorescence (figures 1g, h and i). From the infrared spectrum and the powder diffraction pattern at 25-200 ℃, the peak shape and the peak position are not greatly changed, which indicates that the tetra-polyanion structural skeleton of the material is still unchanged except for losing part of crystal water molecules. V (W-O) in the infrared spectrum due to loss of all the water of crystallization and the coordinated water when the temperature is heated to 400 deg.Ct)、ν(W–Ob)、ν(W–Oc) V (Te-O)a) The four vibration peaks begin to change, and simultaneously, the powder diffraction pattern of the material becomes very poor, most of the characteristic diffraction peaks disappear, and the color of the sample also changes from pink to black. When the temperature rises to 600 to 750 ℃, the characteristic peak of the tellurium tungstate oxolate frame and the peaks of crystal water, coordinated water and dimethylamine on the infrared spectrum completely disappear, and the powder diffraction pattern is 30 DEGoNew diffraction peaks appeared on the left and right, suggesting the formation of new phases (fig. 1g, h). For temperature-variable fluorescence, the fluorescence intensity of the compound is basically kept unchanged within 25-200 ℃, and when the temperature is raised to 400 ℃, the tellurium-tungsten oxysalt frame of the sample collapses, and the fluorescence intensity disappears; when the temperature was raised to 600 to 750 ℃, the characteristic fluorescence intensity increased due to the formation of a new phase (fig. 1 i). This result is consistent with thermogravimetric analysis.
The invention functionalizes the dimethyl tin and comprises { B- α -TeW7O28And { W }5O18The infrared spectrum (see figure 2) and the thermal analysis behavior (see figure 3) of the erbium-embedded tellurium tungstate material of the mixed building block are characterized. Its infrared spectrum is 945, 886, 794, 761, 736, 656 and 702 cm–1The position of the probe has a characteristic peak which is attributed to terminal oxygen v (W-O)t) And bridge oxygen v (W-O)b)、ν(W–Oc) V (Te-O)a) The stretching vibration of (2). Located in the high wavenumber region 1405-1232 cm−1The absorption peak in between is attributed to bending vibration of the methyl group in organotin. Bending vibration of amino and methyl groups in dimethylamine occurred at 3145-3437 cm−1And 2807 + 2452 cm−1In the meantime. 3476 and 3433 cm−1The broad peak at which this occurs corresponds to the stretching vibration and bending vibration of v (O-H) in the crystal water or the coordinated water, which is consistent with the results of single crystal analysis thereof, and further, the dimethyltin is functionalized and contains { B- α -TeW }7O28And { W }5O18The thermal analysis curve of the mixed building block erbium-embedded tellurium tungstate material (1-Er) can be divided into two weight loss processes: the weight loss in the first step from 25 ℃ to 170 ℃ was 4.61% (theoretical 4.04%), corresponding to the loss of 18 crystalline water molecules; the weight loss in the second step from 170 ℃ to 800 ℃ was 7.94%, corresponding to two CH' s3 +The loss of a molecule with an ion carrying one O atom, sixteen protonated hydrogen protons and eight dimethylamine atoms (theoretical 8.46%).
In the present invention, the dimethyltin is functionalized and comprises { B- α -TeW }7O28And { W }5O18The potential application of the Er-embedded tellurium tungstate material 1-Er in the luminescence field of the mixed building block is detected, and the fluorescence emission behaviors of Er/Yb co-doped tellurium tungstate material 1-Er/Yb in different proportions in a visible region and a near infrared region are detected, so that the tellurium tungstate material 1-Er/Yb co-doped with Er/Yb =0.06:0.94 (mass ratio) has an up-conversion luminescence behavior.
In order to discuss the fluorescence property of the Er/Yb co-doped tellurium tungstate material 1-Er/Yb, fluorescence emission and fluorescence service life tests are carried out on the Er/Yb co-doped tellurium tungstate material 1-Er/Yb with different proportions in a visible region and a near infrared region, and a 980 nm laser is used for testing the fluorescence emission behavior converted on the material. As can be seen from FIG. 4a, with Yb3+The increase of ions leads the change trend of the characteristic emission peak intensity of the Er/Yb co-doped tellurium tungstate material 1-Er/Yb in a visible region to be increased and then reduced, and Er (NO) when the characteristic emission peak intensity is strongest3)3·6H2O and Yb (NO)3)3·6H2The optimum ratio of O is 0.40:0.60, probably because of Yb3+The ions can be used as an ideal sensitizer to effectively transfer absorbed energy to Er3+On the ions. Wherein the intensity of the emission peak at 558 nm is also shown firstIncreasing followed by a decreasing trend (fig. 4 b). As can be seen from FIG. 4c, with Yb3+The increase of ions leads the characteristic emission peak intensity of the Er/Yb co-doped tellurium tungstate material 1-Er/Yb in the near infrared region to be gradually reduced, and the main reason is that the Yb in the near infrared region3+Ion insensitivity of Er3+The luminescence of the ions, resulting in a reduction in the intensity of the emission peak. The intensity of the emission peak at 1532 nm showed a tendency to decrease gradually (FIG. 4 d). Similarly, the decay curve and the average lifetime trend of the fluorescence lifetime are consistent with the trend of the strongest emission intensity of the fluorescence (FIGS. 5a, b, c, d).
Anti-Stokes luminescence (Anti-Stokes) follows Stokes law. Stokes law states that a material can only be excited by high-energy light and emit low-energy light. However, it has been found later that some materials can actually achieve the opposite effect of the above-mentioned law, and thus are called anti-stokes luminescence and up-conversion luminescence. In order to investigate whether the tellurium tungstate material 1-Er/Yb is doped with the light with the up-conversion luminescence behavior, the emission behaviors of the Er/Yb doped with the tellurium tungstate materials 1-Er/Yb with different proportions are tested under the excitation of 980 nm light at room temperature. As can be seen from FIG. 6a, the emission spectrum has a very weak emission peak at 531 nm, corresponding to Er3+Of ions2H11/2→4I15/2The emission band at 554 nm, corresponding to Er3+Of ions4S3/2→4I15/2And (4) transition. Along with Yb in the entire upconversion luminescence spectrum3+The intensity of the emission peak of the ion is increased sharply and then further decreased when the ion content is increased, when the Er (NO) content is increased3)3·6H2O and Yb (NO)3)3·6H2When the mass ratio of the O doping reaches 0.06:0.94, the characteristic fluorescence intensity is maximum. From fig. 6b we can see that the intensity of the characteristic emission peak at 531 nm also increases and then decreases, which can be attributed to the cross-relaxation phenomenon. But when Yb3+Although the intensity of the emission peak is gradually increased when the doping concentration of (2) is low, it is difficult to observe in fig. 6b because of the weak cross-relaxationThe relaxation phenomenon has a slight influence on the process of up-conversion luminescence. When Er (NO)3)3·6H2O and Yb (NO)3)3·6H2When the mass ratio of O doping reaches 0.06:0.94, the strong cross relaxation phenomenon in doping causes the emission peak intensity to reach the strongest. However, Yb3+At higher concentrations, a fluorescence quenching phenomenon inevitably occurs, leading to a decrease in the intensity of the up-conversion fluorescence emission. To our knowledge, this is the first time that upconversion luminescence was observed in polyoxometallate materials.
Claims (5)
1. A preparation method of a tellurium tungstate material embedded with dimethyl tin functionalized and containing polyacid mixed building blocks is characterized by comprising the following steps:
mixing Na2WO4·2H2O, dimethylamine hydrochloride, K2TeO3And Sn (CH)3)2Cl2Dissolving in distilled water, adjusting pH to 6.0-6.5, and adding Er (NO)3)3·6H2O or Er (NO)3)3·6H2O and Yb (NO)3)3·6H2O, adjusting the pH value to 6.0-6.5 again, stirring for dissolving, filtering to remove impurities, and volatilizing the filtrate at room temperature to obtain a pink blocky solid which is the tellurium tungstate material;
the Na is2WO4·2H2O, dimethylamine hydrochloride, K2TeO3、Er(NO3)3∙6H2O、Sn(CH3)2Cl2And distilled water in a molar ratio of 10.6 to 16.7: 24.4: 0.78: 1.14-3.82: 1.00: 1660-1670; er (NO)3)3·6H2O and Yb (NO)3)3·6H2The mass ratio of O is 0.96: 0.04-0.02: 0.98.
2. the dimethyltin functionalized tellurium tungstate material which is functionalized and contains polyacid mixed building blocks erbium embedded with tellurium tungstate and prepared by the preparation method of claim 1.
3. Use of the dimethyltin functionalized tellurium tungstate material comprising a polyacid mixture building block erbium embedded in the material of claim 2 in the field of luminescence.
4. Use of a dimethyltin functionalized and polyacid mixture building block erbium-embedded tellurium tungstate material as claimed in claim 3 in the field of luminescence, wherein the tellurium tungstate material is used as the luminescent material.
5. Use of a tellurium tungstate material functionalized with dimethyl tin and containing an erbium insert as defined in claim 3 as a polyacid mixture building block in the field of luminescence, wherein the tellurium tungstate material is used as an up-conversion luminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810686236.3A CN108690605B (en) | 2018-06-28 | 2018-06-28 | Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810686236.3A CN108690605B (en) | 2018-06-28 | 2018-06-28 | Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108690605A CN108690605A (en) | 2018-10-23 |
| CN108690605B true CN108690605B (en) | 2020-10-02 |
Family
ID=63850040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810686236.3A Active CN108690605B (en) | 2018-06-28 | 2018-06-28 | Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690605B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229194B (en) * | 2019-06-27 | 2021-09-07 | 河南大学 | Antimony tungstate material with dysprosium ions and antimony ions bridged simultaneously, and preparation method and application thereof |
| CN111088037B (en) * | 2020-01-13 | 2021-04-23 | 河南大学 | Flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material and preparation method and application thereof |
| CN113929145B (en) * | 2021-10-21 | 2023-03-31 | 河南大学 | Erbium ion embedded arsenic-tungsten oxygen cluster material, preparation method and application |
| CN114772647B (en) * | 2022-05-24 | 2023-06-23 | 河南大学 | Uranium-containing bismuth tungstate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058516A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院上海光学精密机械研究所 | High-concentration erbium ion doped tellurium tungstate glass capable of emitting light at mid-infrared 2.7 microns |
-
2018
- 2018-06-28 CN CN201810686236.3A patent/CN108690605B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058516A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院上海光学精密机械研究所 | High-concentration erbium ion doped tellurium tungstate glass capable of emitting light at mid-infrared 2.7 microns |
Non-Patent Citations (5)
| Title |
|---|
| Assembly of tetrameric dimethyltin-functionalized selenotungstates: from nanoclusters to one dimensional chains;Wei-Chao Chen 等;《Chem. Commun.》;20141231;第51卷;2433-2436 * |
| Rare-Earth-Incorporated Tellurotungstate Hybrids Functionalized by 2‑Picolinic Acid Ligands: Syntheses, Structures, and Properties;Qing Han 等;《Inorg. Chem.》;20171019;第56卷;13228-13240 * |
| Tellurotungstate-Based Organotin−Rare-Earth Heterometallic Hybrids with Four Organic Components;Qing Han等;《Inorg. Chem.》;20170605;第56卷;7257-7269 * |
| 稀土/异金属嵌入碲钨酸盐簇聚物的合成、结构及发光性能研究;韩庆;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20180615;全文 * |
| 稀土取代的新型多钨氧酸盐的合成、结构及性质研究;李海楼;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170315;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108690605A (en) | 2018-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108690605B (en) | Dimethyl tin functionalized tellurium tungstate material embedded with polyacid mixed building block erbium, and preparation method and application thereof | |
| Einkauf et al. | A general model of sensitized luminescence in lanthanide-based coordination polymers and metal–organic framework materials | |
| Yang et al. | Fabrication and luminescence of BiPO4: Tb3+/Ce3+ nanofibers by electrospinning | |
| Wang et al. | Effect of flexible bis-pyridyl-bis-amide ligands and dicarboxylates on the assembly and properties of multifunctional Cu (II) metal–organic coordination polymers | |
| Reddy et al. | Lanthanide benzoates: a versatile building block for the construction of efficient light emitting materials | |
| Hou et al. | A novel family of 3D photoluminescent lanthanide–bta–flexible MOFs constructed from 1, 2, 4, 5-benzenetetracarboxylic acid and different spanning of dicarboxylate acid ligands | |
| Xie et al. | Tunable 4f/5f bimodal emission in europium-incorporated uranyl coordination polymers | |
| Liang et al. | Assembly of lanthanide-containing polyoxotantalate clusters with efficient photoluminescence properties | |
| Gupta et al. | Lanthanoid containing phosphotungstates: the syntheses, crystal structure, electrochemistry, photoluminescence and magnetic properties | |
| Amghouz et al. | Metal organic frameworks assembled from Y (III), Na (I), and chiral flexible-achiral rigid dicarboxylates | |
| Liu et al. | First dimethyltin-functionalized rare-earth incorporated tellurotungstates consisting of {B-α-TeW7O28} and {W5O18} mixed building units | |
| Liu et al. | Two novel donor–acceptor hybrid heterostructures with enhanced visible-light photocatalytic properties | |
| Xia et al. | Ultrasensitive Fe3+ luminescence sensing and supercapacitor performances of a triphenylamine-based TbIII-MOF | |
| Sun et al. | Combining dual-light emissions to achieve efficient broadband yellowish-green luminescence in one-dimensional hybrid lead halides | |
| Pinatti et al. | Tailoring Bi2MoO6 by Eu3+ incorporation for enhanced photoluminescence emissions | |
| Xu et al. | A multi-stimuli-responsive metallohydrogel applied in chiral recognition, adsorption of poisonous anions, and construction of various chiral metal–organic frameworks | |
| Chen et al. | A series of novel lanthanide carboxyphosphonates with a 3D framework structure: synthesis, structure, and luminescent and magnetic properties | |
| Patterson et al. | Lighting Up Two-Dimensional Lanthanide Phosphonates: Tunable Structure–Property Relationships toward Visible and Near-Infrared Emitters | |
| Yu et al. | Fabrication of Er 3+-doped LaOCl nanostructures with upconversion and near-infrared luminescence performances | |
| CN115260517B (en) | Two-dimensional organic-inorganic hybrid polyacid-based high-nuclear rare earth derivative and preparation thereof | |
| Yang et al. | Enhancement of the luminescence properties of high-nuclearity Cd–Ln (Ln= Eu and Nd) nanoclusters by the introduction of more energy transfer donors | |
| Wang et al. | Synthesis, crystal structures and properties of three rare earth substituted germanotungstates: M/[α-GeW11O39](M= Nd, Eu, and Tb) | |
| WO2011064139A2 (en) | Luminescent hybrid liquid crystal | |
| Lv et al. | Preparation of Bitter Melon-like Ordered Porous Fluorinated Eu3+–Phenanthroline/ZnO Composite with Yellow Light Emission | |
| Liu et al. | Molecular design of luminescent halogeno-thiocyano-d 10 metal complexes with in situ formation of the thiocyanate ligand |
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 |