CN105646556B - The preparation method and application of porous rare earth metal organic framework compound - Google Patents
The preparation method and application of porous rare earth metal organic framework compound Download PDFInfo
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- CN105646556B CN105646556B CN201610172518.2A CN201610172518A CN105646556B CN 105646556 B CN105646556 B CN 105646556B CN 201610172518 A CN201610172518 A CN 201610172518A CN 105646556 B CN105646556 B CN 105646556B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The present invention relates to the preparation method and application of porous rare earth metal organic framework compound.The technical scheme of use is：By Ln (NO3)3·6H2O, terephthalic acid (TPA) and o-fluorobenzoic acid are added in the vial of high temperature resistant spiral mouth, then add N, N dimethylformamides, water and concentrated nitric acid, ultrasound is uniformly；It is put into baking oven after vial is sealed, is kept for 24 days at 100 110 DEG C.It is slowly cooled to room temperature, obtains hexa-prism crystal, washing, filter and dry, obtain target product.A series of porous rare earth metal organic framework compounds prepared by the present invention are as detection Fe3+Fluorescence probe, there is good application performance.
Description
Technical field
The present invention relates to a series of porous rare earth metal organic framework compounds, specifically, are related to a series of LnIII(Ln
=Tb, Eu, Dy, Er, Sm, Yb, Gd) and H2The porous rare earth metal organic framework compound that BDC is constructed is as detection Fe3+It is glimmering
Light probe, there is good application performance.
Background technology
In recent years, metal organic framework compound (MOFs) as a kind of new hybrid material more and more by big
The concern of family, it shows huge in the field such as gas storage and capture, separation, chemical catalysis, fluorescence, magnetic and drug delivery
Potential using value.Because MOFs materials can systematically be adjusted by the various combination of metal ion and organic linker
Duct in framework, and the offunctional site in framework can provide platform for specific recognition, and these distinctive functions make
Obtaining MOFs turns into a kind of material of great future.Recently, rare earth metal organic framework compounds (Ln-MOFs) are as detection metal
Oneself is widely studied the fluorescence probe of ion, and the stable duct of Ln-MOFs materials and the synergistic function of photoluminescent property become
A kind of very promising new material.
The content of the invention
The purpose of the present invention is by the use of three core rare earth clusters as node, utilizes terephthalic acid (TPA) (H2BDC) match somebody with somebody as organic
Body, at a certain temperature, utilize a series of porous rare earth metal organic framework compounds of solvent structure.
The technical solution adopted by the present invention is：The preparation method of porous rare earth metal organic framework compound, including it is following
Synthesis step：
1) by Ln (NO3)3·6H2O (Ln=Tb, Eu, Dy, Er, Sm, Yb, Gd), H2BDC, o-fluorobenzoic acid, N, N- diformazans
Base formamide, water and concentrated nitric acid are added in the vial of high temperature resistant spiral mouth, and ultrasound is uniformly；
2) it is put into after vial is sealed in baking oven, is kept for 2-4 days at 100-110 DEG C；
3) it is slowly cooled to room temperature, obtains hexa-prism crystal complex；Preferably, it is described to be slowly cooled to room temperature
Rate of temperature fall is 15-20 DEG C of h-1；
4) cleaned, filtered with DMF, dried, obtain target product.
The synthetic route of the present invention is as shown in figure 1, the knot for the porous rare earth metal organic framework compound that the present invention synthesizes
Structure is as shown in figure 3, the crystal structure belongs to P-3 space groups.Molecular formula is：[Ln3(μ3-OH)(BDC)3(H2O)9]·3DMF·
4H2O (Ln=Tb, Eu, Dy, Er, Sm, Yb, Gd).The compound is by three coordination mode identical LnIIIWith μ3- OH groups
A three core clusters are formed centered on oxygen atom, using the three core cluster as node, three-dimensional pore space structure is formed by dicarboxylates bridging,
As shown in Fig. 2 LnIIIPossess two oxygen atoms in different BDC parts, the oxygen atom of three water of coordination molecule, one is come
From μ3The structure for one eight connection that the oxygen atom of-OH groups is formed, along c-axis direction, the pore size of structure is
The beneficial effects of the invention are as follows：Porous rare earth metal organic framework compound prepared by the present invention can be used as main body
Material is used for the rear synthesis field of host-guest chemistry.Prepared porous rare earth metal organic framework compound can be used as detection
Fe3+Fluorescence probe, there is good application performance.The preparation method of the porous rare earth metal organic framework compound of the present invention
Simply, have great application prospect.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of porous rare earth metal organic framework compound of the present invention.
Fig. 2 is Ln inside porous rare earth metal organic framework compound of the present inventionIII(Ln=Tb, Eu, Dy, Er, Sm, Yb,
Gd) eight connection structure diagrams formed with the oxygen atom of separate sources.
Fig. 3 is the three-dimensional hole structure chart of porous rare earth metal organic framework compound of the present invention.
Fig. 4 is that the present invention is based on TbIIIPorous rare earth metal organic framework compound fluorescence spectra.
Fig. 5 is that different metal ions are based on Tb to the present inventionIIIPorous rare earth metal organic framework compound fluorescence it is strong
Spend block diagram.
Fig. 6 is to add not same amount Fe3+Tb is based on to the present inventionIIIPorous rare earth metal-organic framework materials fluorescence hair
Penetrate spectrogram.
Embodiment
Embodiment 1 is based on TbIIIPorous rare earth metal organic framework compound
By 18.6mg Tb (NO3)3·6H2O, 9.4mg H2BDC and 48.7mg o-fluorobenzoic acid is added to 5mL volumes
High temperature resistant spiral mouth vial in, then add 2.2mL DMF, 0.5mL water and 0.3mL's
Concentrated nitric acid, ultrasound are put into baking oven, kept for 3 days at 105 DEG C, with 15-20 to dissolving for 30 minutes after vial is sealed
℃·h-1Rate of temperature fall be slowly cooled to room temperature, obtained product is cleaned with DMF, filter and dry, most
Obtain eventually colourless hexa-prism based on TbIIIPorous rare earth metal organic framework compound, yield 65%.
The present embodiment synthesis based on TbIIIPorous rare earth metal organic framework compound structure as shown in figure 3, should
Crystal structure belongs to P-3 space groups.Molecular formula is：[Tb3(μ3-OH)(BDC)3(H2O)9]·3DMF·4H2O.The compound is
By three coordination mode identical TbIIIWith μ3Centered on the oxygen atom of-OH groups formed a three core clusters, using the three core cluster as
Node, three-dimensional pore space structure is formed by dicarboxylates bridging, as shown in Fig. 2 TbIIIPossess two to come from different BDC parts
Oxygen atom, the oxygen atom of three water of coordination molecule, one comes from μ3One eight connection that the oxygen atom of-OH groups is formed
Structure, along c-axis direction, the pore size of structure is
The porous rare earth metal organic framework compound of embodiment 2
Method is with embodiment 1, and it is Eu, Dy, Er, Sm, Yb, Gd simply to change Ln ions, as a result as shown in table 1.
Table 1
| Yield % | |
| Eu(NO3)3·6H2O | 67 |
| Dy(NO3)3·6H2O | 58 |
| Er(NO3)3·6H2O | 77 |
| Sm(NO3)3·6H2O | 53 |
| Yb(NO3)3·6H2O | 62 |
| Gd(NO3)3·6H2O | 65 |
Embodiment 3 is based on TbIIIPorous rare earth metal organic framework compound metal ion is entered as ion probe
Row detection
Method：With the preparation of embodiment 1 based on TbIIIPorous rare earth metal organic framework compound as metal ion
Probe is to Fe3+Detected.
1) Fig. 4 is to be based on TbIIIPorous rare earth metal organic framework compound fluorescence emission spectrogram of compound, Fig. 4 shows this
There is green characteristic transmitting, corresponding to Tb under the exciting of 275nm wavelength in materialIIIIon5D4→7FJ(J=3-6) is special
Levy transition.Strong transmitting at 489 and 543nm derives from5D4→7F6With5D4→7F5Transition, at 583 and 621nm compared with
Weak transmitting derives from5D4→7F4With5D4→7F3Transition.
2) Example 1 prepare based on TbIIIPorous rare earth metal organic framework compound, with mortar it is finely ground after with
DMF is configured to 200mL concentration as 10-4Mol/L suspension.Suspension 5mL is taken respectively, is added thereto
20 μ L concentration are 2.5 × 10-2Nitrate M (the NO of mol/L different metal cation3)x(Mx+=Cd2+、Co2+、Cr3+、Mg2 +、Na+、Ni2+、Pb2+、Zn2+、Fe3+) DMF solution, stir under normal temperature, survey their liquid respectively
Fluorescence spectrum, obtaining result, to be depicted as block diagram as shown in Figure 5.As shown in Figure 5, when adding Fe in system3+During solution, cause crystalline substance
The strong quenching (80%) of body fluorescence；And fluorescence intensity influence of other metal ions on crystal be not notable, show Fe3+To this
Invention crystal probe has selectivity well, and sensitive determination Fe can be established based on this3+Analysis method.
3) in order to investigate the Fe of various concentrations3+System Quenching of fluorescence is acted on, then takes suspension 5mL to instill 0 μ L respectively,
1 μ L, 3 μ L, 5 μ L, 10 μ L, 15 μ L, 20 μ L, 30 μ L concentration are 2.5 × 10-2Mol/L Fe (NO3)3N, N- dimethyl formyls
Amine aqueous solution, surveys their fluorescent liquid spectrum respectively after stirring, obtained result is as shown in Figure 6.It will be appreciated from fig. 6 that system
Fluorescence intensity with Fe3+The increase of addition and weaken, as the Fe added in system3+Measure for 30 μ L when, the quenching degree of system
Reach 96%, show crystal probe of the present invention for Fe3+With good Detection results, and detection method have it is simple to operate
The features such as low with test limit, testing result is satisfactory.
Claims (3)
1. porous rare earth metal organic framework compound, it is characterised in that：Described porous rare earth metal organic framework compound
Preparation method, including following synthesis step：
1) by Ln (NO3)3·6H2O, terephthalic acid (TPA), o-fluorobenzoic acid, DMF, water and concentrated nitric acid are added to
In glass containers, ultrasound is uniformly；
2) it is put into after vial is sealed in baking oven, is kept for 2-4 days at 100-110 DEG C；
3) it is slowly cooled to room temperature, obtains intermediate product；
4) intermediate product is cleaned with DMF, is filtered, and is dried, is obtained target product；
The structure of described porous rare earth metal organic framework compound belongs to P-3 space groups, and molecular formula is：[Ln3(μ3-OH)
(BDC)3(H2O)9]·3DMF·4H2O, by three coordination mode identical LnIIIWith μ3Formed centered on the oxygen atom of-OH groups
One three core cluster, using the three core cluster as node, the three-dimensional pore space structure that is formed by dicarboxylates bridging；Wherein, LnIIIPossess
Two oxygen atoms in different BDC parts, the oxygen atom of three water of coordination molecule, one comes from μ3The oxygen of-OH groups is former
The structure for one eight connection that son is formed, along c-axis direction, the duct of described porous rare earth metal-organic framework materials structure
Size is
Described Ln=Tb, Eu, Dy, Er, Sm, Yb or Gd；
The described rate of temperature fall being slowly cooled to room temperature is 15-20 DEG C of h-1。
2. the porous rare earth metal organic framework compound described in claim 1 is as fluorescence probe in detection Fe3+In application.
3. application according to claim 2, it is characterised in that method is as follows：In containing Fe3+Solution in, add right will
The DMF solution of the porous rare earth metal organic framework compound described in 1 is sought, fluorescence is carried out after stirring
Spectral detection.
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| CN106188110B (en) * | 2016-07-13 | 2019-05-17 | 北京化工大学 | A kind of metal-organic framework functional fluorescence material and preparation method and applications |
| CN106008992B (en) * | 2016-07-13 | 2019-05-14 | 郑州轻工业学院 | Micropore terbium Base Metal-organic framework material and its preparation method and application |
| CN106397467B (en) * | 2016-08-31 | 2018-07-06 | 北京化工大学 | A kind of metal-organic framework functional fluorescence material, preparation method and applications |
| CN107556486B (en) * | 2017-08-24 | 2020-08-18 | 中国计量大学 | Rare earth organic framework material for iron ion fluorescence detection and preparation method thereof |
| CN108912463B (en) * | 2018-08-06 | 2021-04-27 | 中国科学院合肥物质科学研究院 | Gadolinium-based metal organic framework composite shielding material and preparation method thereof |
| CN109021247B (en) * | 2018-09-19 | 2021-04-27 | 福州大学 | Rare earth-based metal organic framework compound with lamellar structure and preparation method and application thereof |
| CN112646191B (en) * | 2019-10-12 | 2022-03-22 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN111647168B (en) * | 2020-07-13 | 2022-01-18 | 衡阳师范学院 | Rare earth terbium (III) coordination polymer and preparation method and application thereof |
| CN112382351B (en) * | 2020-10-30 | 2022-03-25 | 华南理工大学 | Method for controllably generating defect mesh framework material model based on computer simulation |
| CN114002201A (en) * | 2021-11-09 | 2022-02-01 | 山西聚微天成科技有限公司 | High-sensitivity ion detection device and application thereof |
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