CN105860961A - Infrared luminescent material for rare-earth metal-organic framework - Google Patents
Infrared luminescent material for rare-earth metal-organic framework Download PDFInfo
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- CN105860961A CN105860961A CN201610307136.6A CN201610307136A CN105860961A CN 105860961 A CN105860961 A CN 105860961A CN 201610307136 A CN201610307136 A CN 201610307136A CN 105860961 A CN105860961 A CN 105860961A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C08G83/008—Supramolecular polymers
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- 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
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- 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
Abstract
The invention discloses an infrared luminescent material for the rare-earth metal-organic framework, and a preparation method of the infrared luminescent material. The molecular structure formula of the infrared luminescent material is [Nd (SnL3)2 (H2O)3] n.n [(H2O)4 (H3O)], where L is ethyl mercaptan acid radical anions with two negative charges, and n is the number of units of high polymer structure. In the structure formula, [Nd (SnL3)2 (H2O)3] n is the metal-organic framework part, n [(H2O)4 (H3O)] is the filler in the framework, and ethyl mercaptan acid radical anions and rare-earth neodymium ions make up of the metal-organic framework of large-hole structure by polymerizing. The infrared luminescent material for the rare-earth metal-organic framework is conveniently prepared at low cost with the hole structure, good luminescence performance and thermal stability through coordinative polymerization of ethyl mercaptan acid radical anions (SnL3-2) and rare-earth ions. The hole structure has large hollow cavities and thermally stable, and can be applied to the technical field of fluorescent sensing detection of various micromolecules.
Description
Technical field
The present invention relates to metal-organic framework material technical field, relate to rare earth metal organic framework materials field, especially
Relate to rare earth metal organic frame field of light emitting materials.
Background technology
Metal organic framework compound (Metal-Organic Frameworks is called for short MOFs) is to be coordinated in recent ten years
Chemical developer obtains a fastest direction, is one and relates to the multi-crossed disciplines such as inorganic chemistry, organic chemistry and Coordinative Chemistry
Hot research field.In terms of the correlative theses quantity that current various main International Periodicals are delivered, MOFs research field proves to be to be worked as
One of focus of front investigation of materials, has wide research and application prospect.On the other hand, right owing to needing in studying at MOFs
The structure of coordination compound, coordination mode, duct size etc. characterize, it is desirable to obtain being suitable for test X in building-up process and penetrate
The crystal of line single crystal diffraction.Which increase the difficulty of MOFs synthesis, thus limit the progress of material development.The research of MOFs is
Along with what the use of clean energy resource and the absorption research of gas were increasingly attracted attention.Currently, due to having absorption
With the urgent needs of the various multi-pore channel materials of the performance such as catalysis, the research of MOFs is promoted to enter the stage of fast development.?
At the MOFs investigation of materials initial stage, the emphasis of research is concentrated mainly on gas absorption and the research of the self assembling process to molecule；Along with
Going deep into MOFs research, the emphasis of research is gradually expanded to magnetics, optics, separation science, catalysis and medicine by gas absorption
The chemical research hot fields such as transmission.Stimulating by the abundant and important potential using value of every field just, MOFs's
Although study on the synthesis difficulty is the least, but still progress is swift and violent.
One of challenge that field of porous materials is prominent is the material that design and synthesis have special construction and high-specific surface area.?
In many actual application, such as the storage etc. of catalyst, separation and gas, such material is all very important.Along with coordination
Chemistry and the development of the direct combinatorial chemistry of metallo-organic compound, novel porous metal-organic framework compound starts appearance.
Porous metal-organic framework compound, i.e. MOFs material, it by metal ion and organic ligand by covalent bond or ionic bond from
Assemble and be built into, be the crystalline state polycrystalline material with regular pore canal or opening structure.Hole in this kind of material has respectively
Kind of shape and size, be the porous material of zeolite and molecular sieve etc observed less than.They have the feature that 1) stronger
Bonding action be that framing structure provides rigidity and stability；2) organic ligand connecting central metal or metal cluster can pass through
Organic synthesis process is adjusted；3) pore structure that skeleton is formed can be controlled by adjusting metal center or organic ligand
System.Owing to having had the advantages such as the stability of easily design control and the inorganic material of organic material concurrently, and there is big ratio table
Area and energy control hole structure, therefore it is at gas and little Molecular Adsorption and separation, selective absorption sensitive material, catalyst etc.
Aspect has the advantage of uniqueness.
The rare earth mining deposits of China is the abundantest, and gross reserves accounts for more than the 40% of the world, and A wide selection of colours and designs, this is rare earth
The application of compound provides huge guarantee.Rare earth compound application is very wide, and it has very at aspect agriculture, industrial, medical
Important application.Therefore the rare-earth products of active development high-tech content, is converted into science and technology competing by the rare earth resources advantage of China
Striving advantage, for promoting industrial transformation and the upgrading of China, and it is the most significant to promote international competitiveness.
Rare earth ion, due to its special electron structure, shows a lot of unique character, thus at optical, electrical, magnetic neck
Territory is all widely used.Design and synthesize and there is the rare earth compounding of high luminous performance be always what researchers were pursued
Target, owing to rare earth ion distinctive 4f electronics is by the bigger shielding action of outer-shell electron so that rare earth ion is by Ligand Field
Affecting the least, so rare earth ion typically has the narrowest characteristic fluorescence to launch, and excitation is high.But the extinction of rare earth ion
Coefficient is the least, needs to carry out by means of " antenna effect " of part the transmission of energy, effectively strengthens the luminescence of rare earth ion.Generally
The anion ligand used has carboxylic acids part and beta-diketon class part, and the neutral ligand as the second assistant ligand is usually
Pyridines or glyoxaline ligand.But, rare earth ion is high coordination of metal ion, and modal ligancy is 8-10, the most past
Toward being accompanied with ligand solvent, such as water or ethanol etc. outside organic ligand, and the existence of these solvents can greatly affect
The luminescent properties of complex material.
The luminescent material of rare earth metal organic framework, is to develop on the basis of rare earth luminescent material and MOFs material
And come.At present, such material has shown that good application prospect in the field such as fluorescent probe, sensor measuring, but material
Kind and performance still have much room for improvement, this remains its key obtaining application at the key areas such as fluorescence sense of restriction and asks
Topic.Therefore research and development luminescent properties and thermally-stabilised good, have the luminous material of the rare earth metal organic framework of good pore passage structure
Material, all has important practical significance for related industries such as exploitation sensing detection.
Summary of the invention
It is an object of the invention to provide infrared lumious material of a kind of rare earth metal organic framework and preparation method thereof.
By the solution generation coordination poly-merization of complex ligand thioglycolic acid stannum anion Yu rare earth ion, convenient and at a low price
Prepare the rare earth metal organic framework infraluminescence material that pore passage structure, luminescent properties and thermal stability are good
Material, its pore passage structure cavity volume is relatively big, Heat stability is good, can be by fluorescence sense detection material technologies such as its various little molecules
Field.
One of technical scheme, is to provide a kind of new rare earth metal organic framework infrared lumious material,
By thioglycolic acid stannum anion (SnL3 2-) obtain with the solution generation coordination poly-merization of rare earth ion, its molecular structural formula
For [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)], in formula L be thioglycolic acid group with two unit negative charge cloudy from
Son, n is the number of repeat unit of Polymer Structure, the similar degree of polymerization；[Nd (SnL in material structure formula3)2(H2O)3]nPart is gold
Belong to organic frame part, n [(H2O)4(H3O)] part is the implant in frame structure.
Described rare earth metal organic framework infrared lumious material is hexagonal crystal system, P63/ m space group, cell parameter isα=90.00 °, β=90.00 °, γ=120.00 °,Z=2, DC=2.471g/cm3, the crystal color of material is lilac；This infrared lumious material structural table
It it is now anionic metal-organic framework feature；Its cationic is the H30 hydroxonium ion being filled in the duct of frame structure
Son, its with as the hydrone that is filled in duct connect by hydrogen bond, present bigger water clustering architecture feature；Anion is then
It it is the metal-organic framework anion of thioglycolic acid stannum anion and rare earth neodymium ionic polymerization composition；The polymerization of this material
Tin ion all three thioglycolic acid groups of chelating ligands in thing anion, use SnO3S3Octahedral build coordination mode；And it is each dilute
Soil neodymium ion all uses NdO9Three cap triangular prism-shaped coordination modes, six of which oxygen comes from neighbouring six thioglycolic acid stannum
Anion, the other three oxygen comes from three waters of coordination.
Described rare earth metal organic framework infrared lumious material is applied to porous material, in the frame structure of this material
Containing the subsphaeroidal cavity of about 1 nanosized, the various little molecule of adsorbable receiving suitable dimension or ion.
Described rare earth metal organic framework infrared lumious material is applied to infrared lumious material, at ultraviolet light and 818
Can launch the characteristic luminescence of neodymium ion under the exciting of nanometer laser, main transmitting peak-to-peak type is sharp-pointed, and peak wavelength is positioned at 1060 and receives
Rice；Secondary emission peak is more weak and wide, and peak wavelength is positioned at 1336 nanometers.
The two of technical scheme, are to provide a kind of rare earth metal organic framework infrared lumious material [Nd
(SnL3)2(H2O)3]n·n[(H2O)4(H3O) preparation method].This preparation method is by thioglycolic acid stannum anion
(SnL3 2-) and the solution generation coordination poly-merization realization of rare earth ion, finally to separate out the product and reality obtaining crystal powder
Existing.Its specific embodiments is divided into three steps:
(1) under room temperature, the sodium salt powder of thioglycolic acid stannum is dissolved in water, obtains settled solution A；
(2) under room temperature, the solid of neodymium nitrate is dissolved in water, obtains settled solution B；
(3) described solution B is added in solution A, continue stirring after having fed and react half an hour, after filtration, filtrate is existed
Evaporate under reduced pressure, filter after waiting a large amount of lilac crystal of precipitation, then with ethanol quick wash twice, be vacuum dried, finally
Obtain a large amount of lilac crystal and be described hybrid material target product.
In preparation method of the present invention, the sodium salt of the two reactant thioglycolic acid stannum: the mol ratio of neodymium nitrate is 2:
1。
First beneficial effects of the present invention is provided rare earth metal organic framework infrared lumious material [Nd
(SnL3)2(H2O)3]n·n[(H2O)4(H3O)], the frame structure of this material contains the subsphaeroidal cavity of about 1 nanosized, can
Absorption accommodates various little molecule or the ion of suitable dimension, can use as adsorbing separation or catalysis material；It addition, described rare earth
Metal-organic framework infrared lumious material, can launch the spy of neodymium ion under the exciting of ultraviolet light and 818 nanometer lasers
Levy infraluminescence, thus can use as infrared lumious material；And in view of this material has pore passage structure and infraluminescence simultaneously
Performance, therefore this material also can use as good sensing material.This material had both possessed advantage that is cheap and that be prone to purification, and
And there is good heat stability, the application further for Hybrid semiconductor material provides technical support.
Beneficial effects of the present invention, next to that prepare rare earth metal organic framework infrared lumious material [Nd (SnL3)2
(H2O)3]n·n[(H2O)4(H3O) method], has simple process, and device therefor is simple, and production cost is low, can be the shortest
Time in obtain the advantages such as the product with very high yield.
Accompanying drawing explanation
Fig. 1. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] divide
The crystallography separate unit mono-crystalline structures figure of son.
Fig. 2. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] divide
The structure chart of thioglycolic acid stannum anion in son.
Fig. 3. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] divide
The coordination mode structure chart of neodymium ion in son.
Fig. 4. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] divide
Son is in unit cell and the accumulation graph of peripheral space.
Fig. 5. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] divide
The accumulation graph that son is shown along c-axis direction, shows obvious pore passage structure.
Fig. 6. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)]
TG-DTA (TG-DSC) analyzes curve, and abscissa represents that temperature, left side vertical coordinate represent that heat, right side vertical coordinate represent weight
Amount percent.
Fig. 7. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)]
Ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 8. rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)] exist
819 nanometer lasers excite under infrared emission light spectrogram.
Detailed description of the invention
The process that realizes of the present invention and the performance of material are illustrated by embodiment:
Embodiment 1
Substantial amounts of rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)]
The preparation of crystal prototype: the sodium salt of the thioglycolic acid stannum weighing 10mmol is dissolved in 40 milliliters of water to obtain settled solution A, weighs
The neodymium nitrate of 5mmol is dissolved in 20 milliliters of water to obtain settled solution B；Then, above-mentioned solution B being added in solution A, charging completes
Half an hour is reacted in rear continuation stirring, by filtrate evaporation under reduced pressure after filtration, separates out a large amount of lilac crystal, waits filtrate to remain
More than filter after about 5 milliliters, then with ethanol quick wash twice, vacuum drying, finally obtain described in a large amount of lilac crystal is
Hybrid material target product, productivity is more than 70%.
Embodiment 2
Synthesizing rare-earth metal-organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)]
Monocrystalline: the sodium salt of the thioglycolic acid stannum weighing 0.2mmol is dissolved in 5 milliliters of water to obtain settled solution A, weighs 0.1mmol's
Neodymium nitrate is dissolved in 3 milliliters of water to obtain settled solution B；Then, above-mentioned solution B is added in solution A, continues after having fed to stir
Mix and react half an hour, after filtration, filtrate is stood at normal temperatures volatilization, has a large amount of lilac platelike crystal to separate out after a few days.Select
The lilac tabular of one 0.32mm*0.18mm*0.15mm size is tested for x-ray crystal structure.The crystallization of this compound
The structure chart learning separate unit is shown graphically in the attached figures 1, and the structure chart of its thioglycolic acid stannum anion is shown graphically in the attached figures 2, joining of neodymium ion
Bit architecture is illustrated in accompanying drawing 3, and its structure cell packed structures is illustrated in accompanying drawing 4, and the pore passage structure of its metal organic frame is illustrated in attached
Fig. 4.
Mono-crystalline structures test shows that described rare earth metal organic framework infrared lumious material belongs to porous material, this material
Containing the subsphaeroidal cavity of about 1 nanosized in the frame structure of material, the various little molecule of adsorbable receiving suitable dimension or from
Son.To rare earth metal organic framework infrared lumious material [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O) pure phase] is brilliant
Body sample has carried out some row performance tests.Material of the present invention has been carried out hot analysis, thermogravimetric-means of differential scanning calorimetry (TG-DSC)
Test shows that this material has preferable stability, and decomposition temperature is close to 300 degrees Celsius, as shown in Figure 5.Brilliant to material of the present invention
Body has carried out steady-state fluorescence test, result show this material can launch under the exciting of ultraviolet light and 818 nanometer lasers neodymium from
The characteristic luminescence of son, main transmitting peak-to-peak type is sharp-pointed, and peak wavelength is positioned at 1060 nanometers, and concrete emission spectrum is as shown in Figure 7.
And this material had both possessed advantage that is cheap and that be prone to purification, also had good heat stability simultaneously.This invention is rare earth gold
The application further belonging to organic framework infrared lumious material provides technical support.
Claims (5)
1. the infrared lumious material of a rare earth metal organic framework, it is characterised in that: the structural formula of infrared lumious material
For [Nd (SnL3)2(H2O)3]n·n[(H2O)4(H3O)], in formula L be thioglycolic acid group with two unit negative charge cloudy from
Son, n is the number of repeat unit of Polymer Structure；[Nd (SnL in material structure formula3)2(H2O)3]nPart is metal organic frame portion
Point, n [(H2O)4(H3O)] part is the implant in frame structure；Described rare earth metal organic framework infrared lumious material
For hexagonal crystal system, P63/ m space group, cell parameter isα=
90.00 °, β=90.00 °, γ=120.00 °,Z=2, DC=2.471g/cm3, the crystal color of material is
Lilac；This infrared lumious material structure shows as anionic metal-organic framework feature；Its cationic is for filling
Hydrogen ion in the duct of frame structure, its with as the hydrone that is filled in duct connect by hydrogen bond, present
Bigger water clustering architecture feature；The metal that anion is then thioglycolic acid stannum anion to be constituted with rare earth neodymium ionic polymerization has
Machine frame structure anion；Tin ion all three thioglycolic acid groups of chelating ligands in the polymer anion of this material, use
SnO3S3Octahedral build coordination mode；And each rare earth neodymium ion uses NdO9Three cap triangular prism-shaped coordination modes, six of which
Oxygen comes from neighbouring six thioglycolic acid stannum anion, and the other three oxygen comes from three waters of coordination.
The preparation method of the infrared lumious material of rare earth metal organic framework the most according to claim 1, its method bag
Include following steps:
(1) under room temperature, the sodium salt powder of thioglycolic acid stannum is dissolved in water, obtains settled solution A；
(2) under room temperature, the solid of neodymium nitrate is dissolved in water, obtains settled solution B；
(3) described solution B is added in solution A, continue stirring after having fed and react half an hour, by filtrate in decompression after filtration
Under the conditions of evaporate, filter after waiting a large amount of lilac crystal of precipitation, then with ethanol quick wash twice, be vacuum dried, finally obtain
A large amount of lilac crystal are described hybrid material target product.
The most according to claim 2, the preparation method of the infrared lumious material of rare earth metal organic framework, its feature exists
In: the sodium salt of the two reactant thioglycolic acid stannum: the mol ratio of neodymium nitrate is 2: 1.
The application of the infrared lumious material of rare earth metal organic framework the most according to claim 1, it is characterised in that institute
Stating rare earth metal organic framework and be applied to porous material, in the frame structure of this material, the duct containing spherical hollow space is tied
Structure, the little molecule of adsorbable receiving and ion, can use as adsorbing separation and catalysis material.
The application of the infrared lumious material of rare earth metal organic framework the most according to claim 1, it is characterised in that institute
State described rare earth metal organic framework infrared lumious material, can launch under the exciting of ultraviolet light and 818 nanometer lasers
The characteristic infrared of neodymium ion is luminous, thus can use as infrared lumious material；And in view of this material has pore passage structure simultaneously
With infraluminescence performance, therefore this material also can use as absorption fluorescent sensing material.
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| CN109437125A (en) * | 2018-10-25 | 2019-03-08 | 临沂大学 | A kind of synthesis annular N5The method of-metal salt |
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| CN102030767A (en) * | 2009-10-06 | 2011-04-27 | 中国计量学院 | Supramolecular metal-organic framework (MOF) compound material |
| CN102617615A (en) * | 2012-02-23 | 2012-08-01 | 山东师范大学 | Metal-organic framework based on rare earth ions, synthetic method for metal-organic framework and application |
| CN103130838A (en) * | 2013-01-11 | 2013-06-05 | 天津师范大学 | Metal-organic frame porous material based on triazole ligand, and preparation method and application thereof |
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| US20100072424A1 (en) * | 2008-09-18 | 2010-03-25 | University Of Pittsburgh--Of The Commonwealth System Of Higher Education | Lanthanide metal-organic frameworks and uses thereof |
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