CN106084247B - A kind of rare earth metal europio organic crystalline material, prepares and its applies - Google Patents
A kind of rare earth metal europio organic crystalline material, prepares and its applies Download PDFInfo
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- CN106084247B CN106084247B CN201610404694.4A CN201610404694A CN106084247B CN 106084247 B CN106084247 B CN 106084247B CN 201610404694 A CN201610404694 A CN 201610404694A CN 106084247 B CN106084247 B CN 106084247B
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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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- 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
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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"
- G01N2021/6432—Quenching
Abstract
The present invention provides a kind of rare earth metal europio organic crystalline material, prepares and its applies, 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 " 1,3,5 three gavaculine of s triazines.The 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.It is an advantage of the invention that：The metal-organic framework materials synthesis technique is simple, crystallization purity is high；Structure is novel, there is high stability in organic solvent；Appraise at the current rate iron ion Fe is recognized simultaneously can2+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 materials,
Specifically with triazine polycarboxylic acid as part, the metal-organic framework material that formed for metal center of Rare Earth Europium, and the chemical combination
Thing by the fluorescence intensity in the solution system containing different metal ions, come the ferrum for 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) get most of the attention, this is perfectly combined the fluorescence feature of lanthanide ion and the porous of MOFs mainly due to it
Together.Metal center of the lanthanide ion as Ln-MOFs, is provided for good photoluminescent property, mainly due to group of the lanthanides from
The fluorescence of son has Stokes (Stokes) displacement big, and glow color purity is high, fluorescence lifetime length and red (Eu3+), green
(Tb3+), indigo plant (Eu2+) three primary colours various the characteristics of.For a lot of Ln-MOFs, the realization of their fluorescence detection functions will also
It is fixed against the duct that guest molecule (including anion, metal cation and organic molecule) is entered in skeleton.Thus, construct
The first step of Ln-MOFs fluorescent probes is exactly to enable guest molecule access aperture by the size of crystal engineering adjustment aperture
Road.The purpose interacted with specific guest molecule can be played by the regulation of device to hole road shape and inner surfaces of pores environment.
In addition, there is site or the exposed metal of lewis acid or alkalescence on the functional groups on skeleton, such as organic ligand
Site, can form hydrogen bond, coordination or π-π and analyte between and interact, and then improve to object identification
Sensitivity.In a word, guest molecule enter main body frame duct inside with organic wall or metal center intimate contact, strengthen
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 materials have been reported, 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, can detect that the fluorescence Ln-MOFs of both organic molecules is more rare simultaneously.It is well 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 that Active transport and passive transport, great majority can be absorbed in the way of passively transporting, and needs carrier protein
And energy, once being absorbed by the somatic cell of human body, blood circulation will be then passed through and be supplied to whole body.But, excessive ferrum is
Poisonous, can cause vomiting, diarrhoea and intestinal are damaged.Fe2+Ion is conducive to the function executing of erythrocyte, can absorb one in human body
Part ion, Fe2+Ion is element needed by human, and is a great number of elements, that is to say, that human body needs more iron ion.
Equally, excessive Fe2+Irritant to respiratory tract, suction causes cough and shortness of breath.Irritant to eyes, skin and mucosa.
Wrongly take cause weakness, stomachache, nausea, have blood in stool, lung and liver are impaired, shock, stupor etc., severe patient can be lethal.There is harm to environment,
Water body can be polluted.For these reasons, realize to Fe3+And Fe2+Selectivity fluorescence identifying get a good eye value.
Content of the invention
The purpose of the present invention is for the above-mentioned state of the art, there is provided a kind of 4,4 ', 4 "-s- triazine -1,3,5- tri--amino
Benzoic acid rare earth Eu metal-organic framework materials and its preparation method and application, the 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 buffer solution3+Presence, can apply
In industrialized production, the metal-organic framework materials synthesis technique is simple, crystallization purity is high；Structure is novel, in organic solvent
In have high stability；Appraise at the current rate iron ion Fe is recognized simultaneously can2+And Fe3+.
A kind of 4,4 ', 4 "-s- triazines three-gavaculines of -1,3,5- rare earth Eu metal-organic framework materials and its conjunctions
Into method and its application, its chemical general formula is：{[Eu(TATAB)(H2O)2] NMP H2O } n, abbreviation Eu-MOF；Wherein, n is represented
Just infinite, TATAB represents 4,4 ', 4, and "-s- triazine -1,3,5- tri--gavaculines, MOF are to tie with metal-organic framework
Structure, the more preferably chemical molecular formula of rare earth metal europio organic crystalline material are C29H30EuN7O10, during its structure such as
Under：
The 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 materials
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 is put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle
Middle mixing, adds 3mLNMP and 2mLH2In the mixed solvent of O, stirring at normal temperature 30min obtains mixed liquor；
(2) above-mentioned mixed liquor is baked at 120 DEG C 72h, solid is separated after taking out product；
(3) above-mentioned solid is washed 3-5 time with NMP, obtains brown lamellar hybrid material crystal.
A kind of 4,4 ', 4 "-s- triazine -1,3,5- three-gavaculine rare earth Eu metal-organic framework materials are used for
Fluorescence identifying in different dicyandiamide solutions to the iron ion rapid sensitive that appraises at the current rate.
It is an advantage of the invention that：The preparation method process is simple, and single crystal form, highly purified crystal material can be obtained
Material；The product structure is novel, and there is higher stability in organic solvent；The product is to Fe2+And Fe3+There is fluorescence identifying
Function, can be used for detect human body buffer in micro Fe2+And Fe3+Presence, compared with traditional detection method, the method
Have qualitative quick, economical, easy.
Description of the drawings
"-s- triazine -1,3,5- three-gavaculine rare earth Eu metals have Fig. 1 prepared by embodiment 1 4,4 ', 4
The two-dimensional layered structure of machine frame crystalline material.
"-s- triazine -1,3,5- three-gavaculine rare earth Eu metals have Fig. 2 prepared by embodiment 1 4,4 ', 4
The solid fluorescence figure of machine frame crystalline material.
Fig. 3 is that crystal prepared by embodiment 1 is acted on and sensitivity to the fluorescence identifying of different metal ions in DMF solution
Detection experiment.Wherein, figure a is 4,4 ', 4 "-s- triazine -1,3,5- tri--gavaculine rare earth Eu metal organic frame crystalline state
Fluorescence intensity figure of the material in selected metal ion DMF suspensions, figure b is for being material in selected metal ion DMF suspensions
In5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 4 (a) be to DMF solution in add variable concentrations Fe2+Figure of fluorescence intensity changes, Fig. 4 (b) is molten to DMF
The Fe of variable concentrations is added in liquid2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 5 (a) be to DMF solution in add variable concentrations Fe2+Figure of fluorescence intensity changes, Fig. 5 (b) is molten to DMF
The Fe of variable concentrations is added in liquid2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 6 is that crystal prepared by embodiment 1 is acted on to the fluorescence identifying of different metal ions and spirit in HEPES aqueous solutions
Sensitivity detection experiment.Wherein, figure a is 4,4 ', 4 "-s- triazine -1,3,5- tri--gavaculine rare earth Eu metal organic frames
Fluorescence intensity figure of the crystalline material in the suspension of selected metal ion HEPES water, figure b is for being material in selected metal ion
In the suspension of HEPES water5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 7 (a) be to HEPES aqueous solutions in add variable concentrations Fe2+Figure of fluorescence intensity changes, Fig. 7 (b) be to
The Fe of variable concentrations is added in HEPES aqueous solutions2+When5D4→7F5Fluorescent emission intensity variation diagram.
Fig. 8 is the powder diffraction after crystal obtained in embodiment 1 is soaked in DMF solution containing different metal ions.
Fig. 9 is the powder diffraction after crystal obtained in embodiment 1 is soaked in the aqueous solutions of HEPES containing different metal ions.
Specific embodiment
Following embodiments is illustrative, is not determinate, it is impossible to limit the guarantor of the present invention with following embodiments
Shield scope.The raw material of the present invention is commercially available.
Raw materials used in embodiment can be obtained from market.Six nitric hydrate europiums, analyze pure, Alpha；4,4′,4″-s-
Analyze pure, Jinan perseveranceization in triazine -1,3,5- tri--gavaculines；NMP, analyzes pure, Jinan perseveranceization；DMF, analyzes pure, Ji
Nan Henghua.
A kind of rare earth metal europio organic crystalline material, prepares and its applies, 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- triazines-
Tri--gavaculines of 1,3,5-.The 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.Characterized in that, the 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 materials
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 is put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle
Middle mixing, adds 3mLNMP and 2mLH2In the mixed solvent of O, stirring at normal temperature 30min obtains mixed liquor；
2) above-mentioned mixed liquor is baked at 120 DEG C 72h, solid is separated after taking out product；
3) above-mentioned solid is washed 3-5 time with NMP, obtains brown lamellar hybrid material crystal.Calculated based on metal Eu
The yield for arriving is 70%.
4,4 ', the 4 "-s- triazine -1,3,5- three-gavaculine rare earth Eu metal organic frame crystal materials that will be prepared
Material 5mg, be added to 10ml containing select different metal ions (Na+、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, room temperature ultrasound shake
0.5h is swung, is taken out, load in the penetrating cuvette in 4ml four sides, fluorescence intensity is tested on fluorophotometric analysiss instrument.With
Sample, will prepare 4,4 ', 4 "-s- triazine -1,3,5- tri--gavaculine rare earth Eu metal organic frame crystalline material 5mg,
Be added to 10ml containing select different metal ions (Na+、K+、Mg2+、Fe3+、Al3+、In3+、Fe2+、Co2+、Ni2+、Mn2 +、Pb2+、Cu2+、Ag+、Zn2+、Cd2+、Hg2+), concentration is 10-2In the HEPES aqueous solutions of mol/L, HEPES is 4- hydroxyethyl piperazines
Ethyl sulfonic acid, HEPES aqueous solutions are human body buffer solution, and suspended aqueous solution room temperature ultrasonic vibration 0.5h takes out, and loads 4ml tetra-
In the penetrating cuvette in face, fluorescence intensity is tested on fluorophotometric analysiss instrument.
The multi-function metal organic framework materials structure and property representation：
1) structure determination of the metal-organic framework material
Crystal structure determination is crystal to be carried out using the small molecule type Advances in crystal X-ray diffraction instrument of Japanese Rigaku companies
Structure determination, using graphite monochromator, the Mo K alpha rays of wavelength X=0.071073nm, measures diffracted intensity and structure cell under 298K
The data such as parameter, and scanning technique is used, empirical absorption correction is carried out to collected data, acquired results adopt Shelxtl-97
Program is parsed with direct method, uses complete matrix least square method correction.Obtain crystallographic data as shown in table 1, structure is shown in Fig. 1 institutes
Show.
Table 1：The crystallographic data of coordination compound
"-s- triazine -1,3,5- three-gavaculine rare earth Eu metals have Fig. 1 prepared by embodiment 1 4,4 ', 4
The single crystal diffraction structure chart of machine frame crystalline material, shows that the material is polymer.
"-s- triazine -1,3,5- three-gavaculine rare earth Eu metals have Fig. 2 prepared by embodiment 1 4,4 ', 4
The solid fluorescence figure of machine frame crystalline material, shows that there is material stronger fluorescence and the feature of rare earth Eu to excite and emission peak
(i.e.：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 the frame structure is characterized：The frame structure is different
The fluorescence identifying of different metal ions is acted in dicyandiamide solution and sensitive detection experiment such as Fig. 3, Fig. 4, Fig. 5, Fig. 6 and Fig. 7
Shown.
From figure 3, it can be seen that in selected metal ion DMF solution, the fluorescence intensity of material is shown to metal ion
Dependency, to Fe2+And Fe3+Show completely fluorescent quenching effect.As can be seen here, the 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 in selected metal ion HEPES
In aqueous solution, the fluorescence intensity of material shows the dependency to metal ion, only Fe3+Show completely fluorescent quenching effect
Really.As can be seen here, the material is containing Fe3+In HEPES aqueous solutions, 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 is adapted to detect for Fe by the phenomenon of fluorescent quenching in DMF solution and HEPES aqueous solutions2+
And Fe3+.As far as we know, this is the first Ln-MOF by identifying the iron ion that appraises at the current rate by different solvents system.
For research material identification Fe in DMF solution2+And Fe3+Sensitivity, the Fe of variable concentrations2+And Fe3+Enter to
In the DMF suspensions of the 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 still present different degrees of downward trend.Their concentration is in 10-7Arrive 10-2During mol/L,
Fluorescence intensity presents linear changing relation, works as Fe2+Concentration in 10-2During mol/L, the fluorescence of material is just quenched substantially completely
Go out；Work as Fe3+Concentration in 10-3During mol/L, the fluorescence of material is just quenched substantially completely.In order to research material identification exists
Fe in HEPES aqueous solutions3+Sensitivity, in HEPES aqueous solutions, equally test variable concentrations Fe3+Fluorescence intensity, find and
Fe in DMF solution3+Concentration is similar to the fluorescence intensity of material, i.e. Fe3+Concentration in 10-3During mol/L, the fluorescence of material is just
Substantially it is quenched completely.Result above shows that the material detects Fe in different solutions system2+And Fe3+During have
Very high sensitivity.
3) stability test：20mg samples are separately immersed in containing the different metal ions that has selected, concentration is 10-2In the DMF solution of mol/L, soak 1 day and filter, solid carries out powder diffraction test with drying in DMF rinse airs.By 20mg
Sample is separately immersed in containing the different metal ions that has selected, and concentration is 10-2In the HEPES aqueous solutions of mol/L, soak 1 day
Filter, solid carries out powder diffraction test with drying in HEPES solution washing air.As shown in Figure 8 and Figure 9, it is institute respectively
Powder diagram of the material after two kinds of solution system immersions containing different metal ions is stated, is shown in figure：The structure energy of material
Holding well is accessed, illustrates that the material has higher stability in both solution systems.
Claims (8)
1. a kind of rare earth metal europio 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- triazines three-gavaculines of -1,3,5-.
2. the rare earth metal europio organic crystalline material described in claim 1, it is characterised in that rare earth metal europio organic crystalline
The chemical molecular formula of material is C29H30EuN7O10, its molecular structural formula is as follows：
3. the rare earth metal europio organic crystalline material described in claim 2, it is characterised in that the crystalline material belongs to monoclinic crystal
It is, space group P21/n space group that cell parameter is： α=90 °, γ
=91.002 (9) °, β=90 °.
4. right wants the preparation method of the rare earth metal europio organic crystalline material described in any one of 1-3, it is characterised in that step
As follows：Under air-proof condition, "-s- triazine -1,3,5- tri--gavaculines are with europium nitrate in N- first for organic ligand 4,4 ', 4
In the mixed solution of base -2-Pyrrolidone and water, via the metal-organic framework material that solvent thermal reaction obtains crystal structure, i.e.,
4,4 ', 4 " three-gavaculines of-s- triazines -1,3,5- rare earth Eu metal-organic framework materials.
5. preparation method according to claim 4, it is characterised in that wherein organic ligand TATAB and europium nitrate mole
Than for 1：1-4, organic ligand 4,4 ', 4 "-s- triazine -1, the corresponding 1ml-5ml of 3,5- tri--gavaculines per 0.5mmol
METHYLPYRROLIDONE and 1ml-4ml deionized water, the condition of thermal response is 100-140 DEG C, and the response 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
Than for 1：2, organic ligand 4,4 ', 4 "-s- triazine -1, the N- first of the corresponding 3ml of 3,5- tri--gavaculines per 0.5mmol
Base -2-Pyrrolidone and the deionized water of 2ml, the condition of thermal response is 120 DEG C, and the response time is 72 hours.
7. application of the rare earth metal europio organic crystalline material described in any one of claim 1-6 on fluorescence identifying.
8. the application described in claim 7, it is characterised in that described rare earth metal europio organic crystalline material is in different solutions
The application that appraises at the current rate in iron ion is recognized in system.
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| CN113527698B (en) * | 2021-06-03 | 2022-07-19 | 西安石油大学 | Europium (III) metal organic framework Eu-MOF probe material and preparation method and application thereof |
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| CN105503915A (en) * | 2015-12-16 | 2016-04-20 | 西北大学 | Europium metal-organic framework compound with fluorescent recognition function and preparation method and application |
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