CN106084247A - A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof - Google Patents
A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof Download PDFInfo
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- 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
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- G—PHYSICS
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- 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"
- G01N2021/6432—Quenching
Abstract
The present invention provides a kind of Rare Earth Europium base organic crystalline material, preparation and application thereof, belongs to the technical field of crystalline material.Chemical molecular formula is { [Eu (TATAB) (H2O)2] NMP H2O}n；Wherein, n represents just infinite, and TATAB represents 4,4 ', 4 " s triazine 1,3,5 three gavaculine.Described metal framework structure elementary cell includes the Eu of a crystallography independence3+Ion and a TATAB part, an Eu3+Ion connects into double-core elementary cell [Eu by six oxygen atoms on three TATAB parts2(CO2)3], double-core unit connects into two-dimensional layer network frame by part.Metal-organic framework materials synthesis technique is simple, crystallization purity is high to the invention have the advantage that this；Novel structure, in organic solvent there is high stability；The iron ion Fe that appraises at the current rate can be identified simultaneously2+And Fe3+。
Description
Technical field
The present invention relates to 4,4 ', 4 "-s-triazine-1,3,5-tri--gavaculine rare earth Eu metal-organic framework material,
Specifically with triazine polycarboxylic acid as part, the metal-organic framework material that formed for metal center of Rare Earth Europium, and this chemical combination
Thing by fluorescence intensity in the solution system of ion containing different metal, come the iron identifying different valence state of rapid sensitive from
Sub-Fe2+And Fe3+。
Background technology
In recent years, various fluorescent sensing materials cause the great interest of people, wherein Lanthanide-metal organic backbone (Ln-
MOFs) getting most of the attention, this perfectly combines the fluorescence feature of lanthanide ion and the porous of MOFs mainly due to it
Together.Lanthanide ion, as the metal center of Ln-MOFs, is provided for good photoluminescent property, mainly due to group of the lanthanides from
It is big that the fluorescence of son has Stokes (Stokes) displacement, and glow color purity is high, fluorescence lifetime length and red (Eu3+), green
(Tb3+), blue (Eu2+) the various feature of three primary colours.For a lot of Ln-MOFs, the realization of their fluorescence detection functions is also wanted
It is fixed against guest molecule (including anion, metal cation and organic molecule) and enter the duct in skeleton.Thus, construct
The size that the first step of Ln-MOFs fluorescent probe is through crystal engineering adjustment aperture enables guest molecule access aperture
Road.By can play the purpose interacting with specific guest molecule to the regulation of duct shape and inner surfaces of pores environment.
In addition, the functional groups on skeleton, such as organic ligand has the site of lewis acid or alkalescence or exposed metal
Site, can and analyte between form hydrogen bond, coordination or π-π interact, and then improve to object identification
Sensitivity.In a word, guest molecule enters inside, duct and organic wall or the metal center intimate contact of main body frame, strengthens
Host-guest interaction.The entrance of guest molecule can affect or change the physicochemical properties of main body frame, including light
Absorption and transmitting etc..
A series of Ln-MOFs fluorescent sensing material has been in the news, their detection range include inorganic metal ion,
Anion, organic molecule pollutant and explosive.But PARA FORMALDEHYDE PRILLS(91,95) and benzaldehyde have the Ln-MOFs fluorescence of detection function
It is few that probe is reported, the fluorescence Ln-MOFs that can simultaneously detect both organic molecules is more rare.It is known that
Fe3+And Fe2+In extensive blood of human body and daily life water, Fe3+Ion can be absorbed by the body with ionic condition,
Absorption pattern includes active transport and passive transport, and great majority can be absorbed in the way of passive transport, needs carrier protein
And energy, once absorbed by the body cell of human body, blood circulation will be then passed through and be supplied to whole body.But, excessive iron is
Poisonous, can cause vomiting, diarrhoea and intestines infringement.Fe2+Ion is conducive to erythrocytic function to perform, and can absorb one in human body
Part ion, Fe2+Ion is the element of needed by human, and is a great number of elements, say, that human body needs more iron ion.
Equally, excessive Fe2+Irritant to respiratory tract, suck and cause cough and breathe hard.Irritant to eyes, skin and mucous membrane.
Wrongly take cause weakness, suffer from abdominal pain, feel sick, have blood in stool, lung and liver is impaired, shock, stupor etc., severe patient can be lethal.Harm is had to environment,
Water body can be polluted.For these reasons, it is achieved to Fe3+And Fe2+Selective fluorescence identifying get a good eye value.
Content of the invention
It is an object of the invention to for the above-mentioned state of the art, a kind of 4,4 ', 4 "-s-triazine-1,3,5-tri--amino are provided
Benzoic acid rare earth Eu metal-organic framework material and its preparation method and application, described metal framework structure elementary cell includes
The Eu of one crystallography independence3+Ion and a TATAB part, an Eu3+Ion is by six on three TATAB parts
Oxygen atom connects into double-core elementary cell [Eu2(CO2)3], double-core unit connects into two-dimensional layer network frame by part.Should
Compound has the function of fluorescence identifying to the iron ion that appraises at the current rate, and can detect micro Fe in human body cushioning liquid3+Existence, can apply
In industrialized production, metal-organic framework materials synthesis technique is simple, crystallization purity is high for this；Novel structure, at organic solvent
In there is high stability；The iron ion Fe that appraises at the current rate can be identified simultaneously2+And Fe3+。
A kind of 4,4 ', 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal-organic framework material and conjunctions thereof
One-tenth method and application thereof, its chemical general formula is: { [Eu (TATAB) (H2O)2] NMP H2O}n, is called for short Eu-MOF；Wherein, n represents
Just infinite, TATAB represents 4,4 ', 4, and " MOF is for having metal-organic framework knot for-s-triazine-1,3,5-tri--gavaculines
Structure, more preferably the chemical molecular formula of Rare Earth Europium base organic crystalline material is C29H30EuN7O10, during its structure such as
Under:
This crystalline material belongs to monoclinic system, and space group is P21/n, and cell parameter is: α=90 °, γ=91.002 (9) °, β=90 °.
Described 4,4 ', the 4 " systems of-s-triazine-1,3,5-three-gavaculine rare earth Eu metal-organic framework material
Preparation Method, with TATAB as part, with NMP and H2O is solvent, and synthesis step is as follows:
(1) by the Eu (NO of 44.5mg3)3·6H2The TATAB of O and 47mg puts into the polytetrafluoroethylliner liner of hydrothermal reaction kettle
Middle mixing, adds 3mLNMP and 2mLH2In the mixed solvent of O, stirring at normal temperature 30min, obtain mixed liquor；
(2) above-mentioned mixed liquor is baked at 120 DEG C 72h, after taking out product, solid is separated；
(3) with NMP, above-mentioned solid is washed 3-5 time, obtain brown sheet hybrid material crystal.
A kind of 4,4 ', 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal-organic framework material is used for
Fluorescence identifying to the iron ion rapid sensitive that appraises at the current rate in different dicyandiamide solutions.
The invention have the advantage that this preparation method technique is simple, and single crystal form, highly purified crystal material can be obtained
Material；This product structure is novel, has higher stability in organic solvent；This product is to Fe2+And Fe3+There is fluorescence identifying
Function, may be used for detection human body buffer solution in micro Fe2+And Fe3+Existence, compared with traditional detection method, the method
There is the qualitative advantage such as quick, economic, easy.
Brief description
Fig. 1 is 4,4 ' prepared by embodiment 1, and 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal has
The two-dimensional layered structure of machine frame crystalline material.
Fig. 2 is 4,4 ' prepared by embodiment 1, and 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal has
The solid fluorescence figure of machine frame crystalline material.
Fig. 3 is fluorescence identifying effect and sensitivity to different metal ion in DMF solution for the crystal prepared by embodiment 1
Detection experiment.Wherein, scheming a is 4,4 ', 4 "-s-triazine-1,3,5-tri--gavaculine rare earth Eu metal organic frame crystalline state
Fluorescence intensity figure in selected metal ion DMF suspension for the material, figure b is for being that material is at selected metal ion DMF suspension
In5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 4 (a) is the Fe adding variable concentrations in DMF solution2+Fluorescence intensity change figure, Fig. 4 (b) is molten to DMF
Liquid adds the Fe of variable concentrations2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 5 (a) is the Fe adding variable concentrations in DMF solution2+Fluorescence intensity change figure, Fig. 5 (b) is molten to DMF
Liquid adds the Fe of variable concentrations2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 6 is fluorescence identifying effect and spirit to different metal ion in the HEPES aqueous solution for the crystal prepared by embodiment 1
Sensitivity detection experiment.Wherein, scheming a is 4,4 ', 4 "-s-triazine-1,3,5-tri--gavaculine rare earth Eu metal organic frames
Fluorescence intensity figure in the suspension of selected metal ion HEPES water for the crystalline material, figure b is for being that material is at selected metal ion
In the suspension of HEPES water5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 7 (a) is the Fe adding variable concentrations in the HEPES aqueous solution2+Fluorescence intensity change figure, Fig. 7 (b) be to
The HEPES aqueous solution adds the Fe of variable concentrations2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 8 is the powder diffraction after the crystal that embodiment 1 prepares soaks in the DMF solution of ion containing different metal.
Fig. 9 is the powder diffraction after the crystal that embodiment 1 prepares soaks in the EPES aqueous solution of IONS OF H containing different metal.
Detailed description of the invention
Following embodiment is illustrative, is not determinate, it is impossible to limit the guarantor of the present invention with following embodiment
Protect scope.The described raw material of the present invention is commercially available.
Raw materials used in embodiment all can obtain from market.Six nitric hydrate europiums, analyze pure, Alpha；4,4′,4″-s-
Triazine-1,3,5-tri--gavaculines, analyze pure, Jinan perseveranceization；NMP, analyzes pure, Jinan perseveranceization；DMF, analyzes pure, Ji
Nan Henghua.
A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof, belong to the technical field of crystalline material.Chemistry
Molecular formula is { [Eu (TATAB) (H2O)2] NMP H2O}n；Wherein, n represents just infinite, and TATAB represents 4,4 ', 4 "-s-triazine-
1,3,5-tri--gavaculine.Described metal framework structure elementary cell includes the Eu of a crystallography independence3+Ion and
One TATAB part, an Eu3+Ion connects into double-core elementary cell by six oxygen atoms on three TATAB parts
[Eu2(CO2)3], double-core unit connects into two-dimensional layer network frame by part.It is characterized in that, this crystalline material belongs to single
Oblique system, space group P21/n space group, cell parameter is: α=
90 °, γ=91.002 (9) °, β=90 °.
Described 4,4 ', the 4 " systems of-s-triazine-1,3,5-three-gavaculine rare earth Eu metal-organic framework material
Preparation Method, with TATAB as part, with NMP and H2O is solvent, and synthesis step is as follows:
1) by the Eu (NO of 44.5mg3)3·6H2The TATAB of O and 47mg puts into the polytetrafluoroethylliner liner of hydrothermal reaction kettle
Middle mixing, adds 3mLNMP and 2mLH2In the mixed solvent of O, stirring at normal temperature 30min, obtain mixed liquor；
2) above-mentioned mixed liquor is baked at 120 DEG C 72h, after taking out product, solid is separated；
3) with NMP, above-mentioned solid is washed 3-5 time, obtain brown sheet hybrid material crystal.Calculate based on metal Eu
To productivity be 70%.
4,4 ', 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal organic frame crystal materials by preparation
Material 5mg, join 10ml contains the different metal ion (Na selecting+、K+、Mg2+、Fe3+、Al3+、In3+、Fe2+、Co2+、
Ni2+、Mn2+、Pb2+、Cu2+、Ag+、Zn2+、Cd2+、Hg2+), concentration is 10-2In the DMF solution system of mol/L, the ultrasonic shake of room temperature
Swing 0.5h, take out, load in the penetrating cuvette in 4ml four sides, fluorophotometric analysis instrument is tested fluorescence intensity.With
Sample, by 4,4 ', the 4 of preparation "-s-triazine-1,3,5-tri--gavaculine rare earth Eu metal organic frame crystalline material 5mg,
Join 10ml contains the different metal ion (Na selecting+、K+、Mg2+、Fe3+、Al3+、In3+、Fe2+、Co2+、Ni2+、Mn2 +、Pb2+、Cu2+、Ag+、Zn2+、Cd2+、Hg2+), concentration is 10-2In the HEPES aqueous solution of mol/L, HEPES is 4-hydroxyethyl piperazine
Ethyl sulfonic acid, the HEPES aqueous solution is human body cushioning liquid, suspended aqueous solution room temperature ultrasonic vibration 0.5h, takes out, loads 4ml tetra-
In the penetrating cuvette in face, fluorophotometric analysis instrument is tested fluorescence intensity.
This multi-function metal organic framework materials structure and property representation:
1) structure determination of this metal-organic framework material
Crystal structure determination is that crystal is carried out by the little molecule-type Advances in crystal X-ray diffraction instrument using Rigaku company of Japan
Structure determination, utilizes graphite monochromator, the Mo K alpha ray of wavelength X=0.071073nm, records diffracted intensity and structure cell under 298K
The data such as parameter, and by scanning technique, carry out empirical absorption correction to collected data, acquired results uses Shelxtl-97
Program resolves with direct method, uses complete matrix least square refinement.Obtaining crystallographic data as shown in table 1, structure is shown in Fig. 1 institute
Show.
Table 1: the crystallographic data of complex
Fig. 1 is 4,4 ' prepared by embodiment 1, and 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal has
The single crystal diffraction structure chart of machine frame crystalline material, shows that this material is polymer.
Fig. 2 is 4,4 ' prepared by embodiment 1, and 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal has
The solid fluorescence figure of machine frame crystalline material, shows that material has stronger fluorescence and the feature of rare earth Eu excites and emission peak
(that is: under 310nm maximum excitation wavelength, its have four feature excitation wavelengths 590nm (5D4→7F6), 612nm (5D4→7F5),
650nm(5D0→7F3), 700nm (5D0→7F4)).2) photoluminescent property of this frame structure characterizes: described frame structure is different
Fluorescence identifying effect and the sensitive detection of different metal ion are tested such as Fig. 3, Fig. 4, Fig. 5, Fig. 6 and Fig. 7 by dicyandiamide solution
Shown in.
From figure 3, it can be seen that in selected metal ion DMF solution, the fluorescence intensity of material shows to metal ion
Dependence, to Fe2+And Fe3+Show fluorescent quenching effect completely.As can be seen here, this material is containing Fe2+And Fe3+DMF
In solution, the phenomenon of this fluorescent quenching is adapted to detect for Fe2+And Fe3+.And from fig. 5, it can be seen that at selected metal ion HEPES
In the aqueous solution, the fluorescence intensity of material shows the dependence to metal ion, only Fe3+Show the effect of fluorescent quenching completely
Really.As can be seen here, this material is containing Fe3+In the HEPES aqueous solution, the phenomenon of this fluorescent quenching is adapted to detect for Fe3+.Comprehensive with
Upper two kinds of situations, it has been found that material, in DMF solution and the HEPES aqueous solution, is adapted to detect for Fe by the phenomenon of fluorescent quenching2+
And Fe3+.As far as we know, this is the first by being identified the Ln-MOF of the iron ion that appraises at the current rate by different solvents system.
For research material identification in DMF solution Fe2+And Fe3+Sensitivity, the Fe of variable concentrations2+And Fe3+Enter to
In the DMF suspension of this material, and have recorded the change of fluorescence intensity.As shown in Figure 4 and Figure 5, the fluorescence intensity of material with
Fe2+And Fe3+Concentration increase and still present downward trend in various degree.Their concentration is at 10-7To 10-2During mol/L,
Fluorescence intensity presents linear changing relation, works as Fe2+Concentration at 10-2During mol/L, the fluorescence of material is just quenched substantially completely
Go out；Work as Fe3+Concentration at 10-3During mol/L, the fluorescence of material is just substantially by complete cancellation.In order to research material identification exists
Fe in the HEPES aqueous solution3+Sensitivity, in the HEPES aqueous solution, test variable concentrations Fe equally3+Fluorescence intensity, discovery and
Fe in DMF solution3+Concentration is similar to the fluorescence intensity of material, i.e. Fe3+Concentration at 10-3During mol/L, the fluorescence of material is just
Substantially by complete cancellation.Result above shows that this material detects Fe in different solutions system2+And Fe3+During have
Very high sensitivity.
3) stability test: being separately immersed in 20mg sample containing the different metal ion selected, concentration is 10-2In the DMF solution of mol/L, soak filtration in 1 day, solid DMF rinse air dries, carries out powder diffraction test.By 20mg
Sample is separately immersed in containing the different metal ion selected, and concentration is 10-2In the HEPES aqueous solution of mol/L, soak 1 day
Filter, solid HEPES solution washing air dries, carries out powder diffraction test.As shown in Figure 8 and Figure 9, it is institute respectively
State powder diagram after the solution system of two kinds of ions containing different metal soaks for the material, figure shows: the structure energy of material
Access well holding, illustrate that this material has higher stability in both solution systems.
Claims (8)
1. a Rare Earth Europium base organic crystalline material, it is characterised in that chemical molecular formula is { [Eu (TATAB) (H2O)2]·
NMP·H2O}n；Wherein, n represents just infinite natural number, and NMP is organic solvent METHYLPYRROLIDONE, and TATAB represents 4,
4 ', 4 "-s-triazine-1,3,5-three-gavaculine.
2. the Rare Earth Europium base organic crystalline material described in claim 1, it is characterised in that Rare Earth Europium base organic crystalline
The chemical molecular formula of material is C29H30EuN7O10, its molecular structural formula is as follows:
3. the Rare Earth Europium base organic crystalline material described in claim 2, it is characterised in that this crystalline material belongs to monoclinic crystal
System, space group P21/n space group, cell parameter is: α=90 °, γ
=91.002 (9) °, β=90 °.
4. right wants the preparation method of the Rare Earth Europium base organic crystalline material described in any one of 1-3, it is characterised in that step
As follows: under air-proof condition, organic ligand 4,4 ', 4 "-s-triazine-1,3,5-tri--gavaculines and europium nitrate are in N-first
Base-2-Pyrrolidone, with the mixed solution of water, obtains the metal-organic framework material of crystal structure, i.e. via solvent thermal reaction
4,4 ', 4 "-s-triazine-1,3,5-three-gavaculine rare earth Eu metal-organic framework material.
5. preparation method according to claim 4, it is characterised in that wherein organic ligand TATAB and europium nitrate mole
Ratio is 1:1-4, the organic ligand 4,4 ' of every 0.5mmol, 4 "-s-triazine-1, the corresponding 1ml-5ml of 3,5-tri--gavaculines
The deionized water of METHYLPYRROLIDONE and 1ml-4ml, the condition of thermal response is 100-140 DEG C, and the reaction time is 60-
80 hours.
6. preparation method according to claim 5, it is characterised in that wherein organic ligand TATAB and europium nitrate mole
Ratio is 1:2, the organic ligand 4,4 ' of every 0.5mmol, 4 "-s-triazine-1, the N-first of the corresponding 3ml of 3,5-tri--gavaculines
Base-2-Pyrrolidone and the deionized water of 2ml, the condition of thermal response is 120 DEG C, and the reaction time is 72 hours.
7. application on fluorescence identifying for the Rare Earth Europium base organic crystalline material described in any one of claim 1-6.
8. the application described in claim 7, it is characterised in that described Rare Earth Europium base organic crystalline material is at different solutions
System identifies the application appraised at the current rate in iron ion.
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| CN106866989A (en) * | 2017-01-20 | 2017-06-20 | 江南大学 | One kind has selectivity detection Fe3+The preparation method of the luminescent crystal material of ion |
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