CN101735798A - Rare earth organic framework material having sensing function to acetone, preparation method and application thereof - Google Patents
Rare earth organic framework material having sensing function to acetone, preparation method and application thereof Download PDFInfo
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- CN101735798A CN101735798A CN200910194155A CN200910194155A CN101735798A CN 101735798 A CN101735798 A CN 101735798A CN 200910194155 A CN200910194155 A CN 200910194155A CN 200910194155 A CN200910194155 A CN 200910194155A CN 101735798 A CN101735798 A CN 101735798A
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Abstract
The invention discloses a rare earth organic framework material having sensing function to acetone, a preparation method and application thereof. The material has the following chemical formula: [Eu(pyca)(ox)0.5(H2O)].4(H2O), wherein, pyca is 2,5-pyrazine diacid ligand, and ox is oxalate ligand. The invention selects 5-methyl-pyrazine-2-carboxylic acid and Eu metal to synthesize a three-dimensional metal organic framework with one-dimensional pore canals. When acetone molecules are added in the N-N'-dimethyl formamide solution of Eu metal containing organic framework, the position of the fluorescence-emission peak is not changed, the strength of the emission peak recedes obviously along with the enhancement of the concentration of the acetone molecule, thus the framework material can be used as a fluorescence probe of acetone molecule to detect trace acetone molecules in the solution. The material has stable structure and strong water-resistance. The invention has convenient, fast and sensitive characteristics in chemical detection.
Description
Technical field
The present invention relates to a kind of rare earth metal organic framework material, particularly relate to acetone is had sensing function and stable rare earth organic framework material and the preparation method of anti-water, can be used as Eu
3+Metal mold acetone molecules fluorescent probe.
Background technology
Detection to volatile organism is very important problem in environmental monitoring and even the daily life aspect, has caused national governments and expert's great attention.Acetone is the widely used volatile organic solvent in a kind of industry and laboratory, and acetone can advance human body through respiratory tract, digestive tube, skin, the serious harm HUMAN HEALTH.In view of the significant damage of acetone to human body, we usually will analyze and measure its content in environmental monitoring work such as pollution incident, environmental impact assessment and facility examination.Quantitative detecting method to acetone gas mainly contains at present: gas phase or liquid phase chromatography, gas chromatography-mass spectrography, colorimetry, quartz crystal micro-balance method, Light Addressable Potentiometric Sensor (LAPS) method, Fiber Optical Sensor Based and oxide semiconductor gas sensor material, fluorescent probe method etc.But gas phase or liquid phase chromatography, gas chromatography-mass spectrography detect that cost is higher, and the time is longer, and colorimetry, the sensitivity of quartz crystal micro-balance method are not high, and error is bigger; The transducer production method complexity of utilizing in the sensor method, the cost height, the oxide semiconductor gas sensor material different metal ion that also will mix wherein, much has toxicity in these ions, environmental pollution is bigger, and working temperature is higher, and zno-based acetone sensitive material for example is when mixing the high acid metal ion W of electronegativity
6+And Mo
6+, when working temperature is 500 ℃, WO
3-ZnO and MoO
3-ZnO can detectable level be the acetone molecules of 20ppm.Relative other detection methods of fluorescent probe method have with low cost, and sensitivity is higher, operates advantages such as simple and easy.Therefore, utilize simple preparation method, synthesize a kind of to acetone molecules have that sensitivity is higher, energy consumption and cost is low, detection means is simple and easy, the material that environmental pollution is little has great importance.
Metal-organic framework materials (MOFs) is a kind of class zeolite with supramolecule microporous network structure (organic zeolite analogue) material that utilizes the metal-ligand complexing action self-assembly between organic ligand and metal ion to form.Wherein the research of rare earth metal organic framework material (LnOFs) receives the concern of vast researcher in recent years.In the rare earth luminescence life-span long (reaching micron dimension), can significantly be different from background fluorescence; Luminescence spectrum is narrow, has very high recognition resolution.These advantages make it have important application value aspect molecular recognition, as can be used as biological fluorescent labeling, detect rare earth ion is photosensitive ionic ionic concn [P.B.Glover etc., J.Am.Chem.Soc., 2003,125,9918].But the stability of existing metal-organic framework materials is generally not high, and particularly easy recurring structure caves under the situation that steam exists, thereby has hindered its practical application (Y.Li etc., Langmuir, 2007,23,12937) greatly.Therefore, it is stable and have highly sensitive rare earth organic framework fluorescent probe to research and develop anti-water, more can satisfy the needs of practical application.
Summary of the invention
The object of the present invention is to provide a kind ofly has sensing function and the stable rare earth metal organic framework material of anti-water to acetone molecules, and it is an europium metal-organic framework materials type acetone molecules fluorescent probe.
Another object of the present invention is to provide above-mentioned acetone molecules that the preparation method of the stable rare earth metal organic framework material of sensing function and anti-water is arranged.
The present invention also has a purpose, is to provide acetone molecules that the application of the stable rare earth metal organic framework material of sensing function and anti-water as the acetone molecules fluorescent probe arranged.
The object of the invention is achieved through the following technical solutions:
A kind of have the rare earth organic framework material of sensing function to acetone, and the chemical formula of this rare earth organic framework material is: [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O), wherein, pyca=2,5-pyrazine diacid part; Ox is the oxalic acid part; Main infrared absorption peak is: 3379cm
-1, 2924cm
-1, 2853cm
-1, 1610cm
-1, 1461cm
-1, 1392cm
-1, 1323cm
-1, 1179cm
-1, 1047cm
-1, 846cm
-1, 778cm
-1, 722cm
-1, 519cm
-1, 483cm
-1This compound is a crystalline structure, and crystal belongs to triclinic(crystalline)system, and spacer is P-1; Unit cell parameters is:
α=68.872 (3) °, β=81.013 (3) °, γ=76.722 (3) °; { [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O) }
nThree-dimensional structure in, each Eu ion with from three carboxylic acid Sauerstoffatoms and two nitrogen-atoms on three different pyca parts, two carboxylic acid Sauerstoffatoms and two water molecules coordinations on oxalate denominationby form the anti-prism configuration in nine coordinate list caps four directions.In this ligand polymer, μ
42 of linear bridging configuration, 5-dicarboxylic acid pyrazine part and oxalate denominationby form adjacent europium (III) ion the laminate structure of two dimension along a direction of principal axis.And μ
62 of bridging configuration, 5-dicarboxylic acid pyrazine part pass through to connect different four europiums (III) ions, thereby two-dimensional layered structure is connected into three-dimensional network structure.Comprising one in the three-dimensional net structure is about
Size is along the axial micropore of a cavity.
Acetone there is the preparation method of the rare earth organic framework material of sensing function, may further comprise the steps:
(a) europium sesquioxide is become nitrate with the concentrated nitric acid acid treatment;
(b) step (a) gained nitrate with water dissolution after, add 5-methyl-pyrazine-2-carboxylic acid and concentrated nitric acid, the mass ratio of water, europium nitrate, 5-methyl-pyrazine-2-carboxylic acid and concentrated nitric acid is (5~500): 4.5: 2.7: (1~5);
(c) step (b) gained mixture is transferred in the polytetrafluoroethylliner liner of hydrothermal reaction kettle, under 120~180 ℃ of conditions, reacted 15~50 hours;
(d) programmed cooling filters and oven dry to room temperature, gets target product; Described programmed cooling is meant that rate of temperature fall is 5~20 ℃/hour.
The mass ratio of described step (1) europium sesquioxide and concentrated nitric acid acid is preferably 1: 50~and 1: 25.
Acetone there be the application of the stable rare earth metal organic framework material of sensing function and anti-water as the acetone molecules fluorescent probe.
The used organic ligand raw material of the present invention is 5-methyl-pyrazine-2-carboxylic acid, and the rare earth metal organic framework material of gained is by 2, and 5-dicarboxylic acid pyrazine part and oxalate part constitute.Because this reaction is to carry out in the highly acid aqueous solution, so the methyl in raw material 5-methyl-pyrazine-2-carboxylic acid is easy to be oxidized to carboxylic acid under High Temperature High Pressure, and the part carboxylic acid that generates easily decarboxylation generate electronegative CO
2 -, per two electronegative CO
2 -Further reaction generates oxalate denominationby.The present invention selects for use 5-methyl-pyrazine-2-carboxylic acid part and europium (Eu) metal to synthesize the 3-dimensional metal organic framework material with one-dimensional channels.When at this N that contains the europium metal-organic framework materials, when adding acetone molecules in N '-dimethyl formamide solution, the invariant position of fluorescence emission peak, the intensity of emission peak significantly weakens along with the enhancing of acetone molecules concentration.Therefore can be used as the fluorescent probe of acetone molecules, detect the trace acetone molecule in the solution.This metal-organic framework materials Stability Analysis of Structures has very strong water resisting property.Therefore, be with a wide range of applications, have easily and fast, sensitive characteristics at the chemical detection range.
Rare earth metal organic framework material of the present invention is synthetic under hydrothermal condition, and is water insoluble, and structure does not have considerable change soak 72h in water after, has very strong water resisting property.Have higher thermostability simultaneously, thermogravimetric analysis shows that only when temperature was higher than 350 ℃, [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O) just can part decompose, these 2 more superior than existing fluorescent material.
Have luminescent lifetime long (reaching micron dimension) based on rare earth ion, can significantly be different from background fluorescence; Luminescence spectrum is narrow, has very high recognition resolution, thereby makes it have advantageous advantage aspect catalysis, molecular recognition, the detection.Effect of Mg ionic and function thereof in researching DNA and the organism have been widely used in as the Tb ion.
Reported in recent years ethanol, N, organic molecules such as N '-dimethyl formamide, acetone have optionally rare earth metal organic framework material type fluorescent probe, when the concentration of these organic molecules increases, can cause the change of corresponding rare earth ion fluorescence intensity, thereby determine such contained organic molecule concentration in the system.The three-dimensional europium metal-organic framework materials that the present invention has one-dimensional channels has the selectivity of height for acetone, and the intensity of rare earth emission peak significantly weakens along with the increase of acetone molecules concentration, when the amount of acetone molecules constantly increases, and emission peak
5D
0→
7F
2Intensity constantly weaken.Because acetone is the water white transparency inflammable liquid, widespread use in industry and scientific research, the space that the present invention will make new advances for the application developing of rare earth metal organic framework material.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) preparation method is simple and easy, sensitivity is higher.This material just can obtain by single step reaction is synthetic, the test shows of acetone is had selectivity discern and higher sensitivity;
(2) energy consumption and cost are low, detection means is simple and easy; This material usage seldom (1mg) just has measuring ability, and operates and finish at normal temperatures, and working method is simple and easy;
(3) environmental pollution is little; This material is the europium metal-organic framework materials, and other any metal ions need not additionally mix.
(4) anti-water is stable.This material is water insoluble, and structure does not have considerable change soak 72h in water after, has higher thermostability simultaneously.
Description of drawings
[Eu (pyca) (ox) for Fig. 1
0.5(H
2O)] 4 (H
2O) unitary crystalline structure figure.
Fig. 2 is in [100] direction, and { [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O) }
nThe three-dimensional net structure figure that comprises the single passage micropore.
Fluorescence emission spectrogram under Fig. 3 europium metal-organic framework materials solid state.
The fluorescence spectrum of Fig. 4 europium metal-organic framework materials under different acetone concentration.
Fig. 5 europium metal-organic framework materials is scattered in the fluorescence intensity after the different organic solvents.
Fig. 6 europium metal-organic framework materials is soaked in the water behind the 72h and the XRD powdery diffractometry spectrogram of new synthetic sample.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but the scope of protection of present invention scope of representing in embodiment of limitation not.
Embodiment 1
A: hydrothermal synthesis method synthesizes The compounds of this invention:
(1) weighing 0.5mmol Eu
2O
3, use the concentrated nitric acid heating for dissolving, volatilization is cooled to europium nitrate;
(2) weighing 1mmol 5-methyl-pyrazine-2-carboxylic acid together is dissolved in the 15ml redistilled water with above-mentioned Eu salt;
(3) add the 0.12ml concentrated nitric acid, transfer in the 23ml hydrothermal reaction kettle after fully stirring;
(4) in 150 ℃ of following isothermal reaction 24h.Then, with 10 ℃ of h
-1Cool to room temperature;
(5) open hydrothermal reaction kettle, get faint yellow bulk crystals, be The compounds of this invention.
B: the structure determination of title complex
Crystalline structure adopts Bruker SMART 1000X-x ray diffractometer x, uses the monochromatization of process graphite to get the MoK alpha-ray
Be incident radiation, collect point diffraction, obtain unit cell parameters, utilize the SHELXL-97 direct method to solve crystalline structure from the difference Fourier electron density map through least-squares refinement with ω-2 θ scan mode, and through Lorentz and polarizing effect correction.All H atoms are synthetic and definite through desirable position calculation by difference Fourier.Table 1 is the detailed data of axonometry, illustrates that this material has following unique texture feature: by metal europium ion, 2, the 5-dicarboxylic acid is more organic framework structured than the 3-dimensional metal with one-dimensional channels of piperazine part and oxalate part formation.
Structure is seen Fig. 1, Fig. 2.Fig. 1: resolve the file that obtains after this crystal data by software xshell, utilize the XP picture function treatment gained file of shelxtl software again, having drawn, [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O) unit crystalline structure figure.Fig. 2: resolve the file that obtains after this crystal data by software xshell, utilize drawing software diamond to handle the gained file again, having drawn, { [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O) }
nThe three-dimensional net structure figure that comprises the single passage micropore.
The crystallographic data of table 1 title complex
R=∑(||F
o|-|F
c||)/∑|F
o|.
wR=[∑w(F
o 2-F
c 2)
2/∑w(F
o)
2]
1/2.
C: the photoluminescent property by title complex detects the identification of acetone
The photoluminescent property of title complex that adopted F-4500FL type fluorescent spectrophotometer assay is measured the spectrum of title complex at solid state, and excitation wavelength is 308nm, has obtained Eu
3+Emmission spectrum (Fig. 3).Emission peak 591,614,649 and 695nm place, can point out respectively into
5D
0→
7F
1,
5D
0→
7F
2,
5D
0→
7F
3,
5D
0→
7F
4Title complex was dried 5 hours down at 130 ℃, when in the acetone molecules of measuring through adding difference in the DMF solution of pretreated title complex, four emission peak peak positions are compared when not adding acetone, any moving do not taken place, but peak intensity is along with the concentration of acetone molecules strengthens and significantly weakens, when adding the acetone molecules of 13% (volume fraction), all peak intensities almost disappear (Fig. 4).And in the organic solvents such as the acetonitrile that the same amount title complex is scattered in, ethanol, Virahol, ether, DMF, chloroform, ethyl acetate, methylene dichloride, toluene, triethylamine or normal hexane the time, fluorescence intensity all changes, but rangeability is far smaller than acetone molecules (Fig. 5).This fluorescence that shows the europium metal-organic framework materials of being invented has highly selective to acetone molecules.
D: the anti-water stability of title complex
Get two parts of 100mg synthetic europium metal-organic framework materials respectively, a copy of it is soaked in the 50ml beaker that contains 10ml distilled water, take out behind the 72h and filter, gained sample and the undressed sample of another part all dry by the fire 2h under 50 ℃ of conditions, two duplicate samples are tested XRD powdery diffractometry (Fig. 6) respectively then.As seen from Figure 6, in water, soak behind the 72h structure and unprocessed structures of samples and do not have significant difference.Illustrate that title complex has very strong anti-water stability.
A: compound synthetic
(1) weighing 0.1mmol Eu
2O
3, use the concentrated nitric acid heating for dissolving, volatilization is cooled to europium nitrate;
(2) weighing 0.2mmol 5-methyl-pyrazine-2-carboxylic acid together is dissolved in the 5ml redistilled water with above-mentioned Eu salt;
(3) add the 0.04ml concentrated nitric acid, transfer in the 23ml hydrothermal reaction kettle after fully stirring;
(4) in 120 ℃ of following isothermal reaction 50h.Then, with 5 ℃ of h
-1Cool to room temperature;
(5) open hydrothermal reaction kettle, get faint yellow bulk crystals, be The compounds of this invention.
B: the structure of compound
Characterize by single crystal diffraction, find that crystal belongs to triclinic(crystalline)system, spacer is P-1, and unit cell parameters is:
α=68.873 (3) °, β=81.013 (2) °, γ=76.721 (3) °.Illustrate with the prepared compound of embodiment 1 be same spline structure.
A: compound synthetic
(1) weighing 0.5mmol Eu
2O
3, use the concentrated nitric acid heating for dissolving, volatilization is cooled to Eu salt;
(2) weighing 1mmol 5-methyl-pyrazine-2-carboxylic acid together is dissolved in the 10ml redistilled water with above-mentioned Eu salt;
(3) add the 0.08ml concentrated nitric acid, transfer in the 23ml hydrothermal reaction kettle after fully stirring;
(4) in 150 ℃ of following isothermal reaction 24h.Then, with 10 ℃ of h
-1Cool to room temperature;
(5) open hydrothermal reaction kettle, get faint yellow bulk crystals, be The compounds of this invention.
B: the structure of compound
Characterize by single crystal diffraction, find that crystal belongs to triclinic(crystalline)system, spacer is P-1, and unit cell parameters is:
α=68.871 (4) °, β=81.012 (3) °, γ=76.722 (2) °.Illustrate with the prepared compound of embodiment 1 be same spline structure.
A: compound synthetic
(1) weighing 1mmol Eu
2O
3, use the concentrated nitric acid heating for dissolving, volatilization is cooled to europium nitrate;
(2) weighing 2mmol 5-methyl-pyrazine-2-carboxylic acid together is dissolved in the 15ml redistilled water with above-mentioned Eu salt;
(3) add the 0.12ml concentrated nitric acid, transfer in the 23ml hydrothermal reaction kettle after fully stirring;
(4) in 180 ℃ of following isothermal reaction 15h.Then, with 20 ℃ of h
-1Cool to room temperature;
(5) open hydrothermal reaction kettle, get faint yellow bulk crystals, be The compounds of this invention.
B: the structure of compound
Characterize by single crystal diffraction, find that crystal belongs to triclinic(crystalline)system, spacer is P-1, and unit cell parameters is:
α=68.875 (2) °, β=81.013 (3) °, γ=76.721 (2) °.Illustrate with the prepared compound of embodiment 1 be same spline structure.
By the title complex of the foregoing description gained, dried 5 hours down in 130 ℃, promptly obtain acetone is had the rare earth organic framework material probe of sensing function after the cooling.Than other detection techniques, present technique has advantages such as the preparation method is simple, detecting operation means simple and convenient, sensitivity is higher, detected temperatures is low (normal temperature), the little and anti-water of material environmental pollution is stable, is with a wide range of applications at the chemical detection range.
Claims (6)
1. one kind has the rare earth organic framework material of sensing function to acetone, and it is characterized in that: the chemical formula of this rare earth organic framework material is: [Eu (pyca) (ox)
0.5(H
2O)] 4 (H
2O), wherein, pyca=2,5-pyrazine diacid part; Ox is the oxalic acid part; This compound is a crystalline structure, and crystal is a triclinic(crystalline)system, and spacer is P-1.
2. according to claim 1 have the rare earth organic framework material of sensing function to acetone, it is characterized in that the unit cell parameters of described rare earth organic framework material is: a=6.0915 (15)
, b=9.961 (2)
, c=13.361 (3)
α=68.872 (3) °, β=81.013 (3) °, γ=76.722 (3) °.
3. according to claim 1 have the rare earth organic framework material of sensing function to acetone, it is characterized in that: acetone is had the selectivity sensing function to this material and anti-water is stable.
4. claim 1 is described has the preparation method of the rare earth organic framework material of sensing function to acetone, it is characterized in that, may further comprise the steps:
(a) europium sesquioxide is become europium nitrate with the concentrated nitric acid acid treatment;
(b) step (a) gained nitrate with water dissolution after, add 5-methyl-pyrazine-2-carboxylic acid and concentrated nitric acid, the mass ratio of water, europium nitrate, 5-methyl-pyrazine-2-carboxylic acid and concentrated nitric acid is (5~500): 4.5: 2.7: (1~5);
(c) step (b) gained mixture is transferred in the polytetrafluoroethylliner liner of hydrothermal reaction kettle, under 120~180 ℃ of conditions, reacted 15~50 hours;
(d) programmed cooling filters and oven dry to room temperature, gets target product; Described programmed cooling is meant that rate of temperature fall is 5~20 ℃/hour.
5. according to claim 4 have the preparation method of the rare earth organic framework material of sensing function to acetone, it is characterized in that the mass ratio of described step (1) europium sesquioxide and concentrated nitric acid acid is 1: 50~1: 25.
6. claim 1 is described has the application of the stable rare earth metal organic framework material of sensing function and anti-water as the acetone molecules fluorescent probe to acetone.
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CN103965230A (en) * | 2014-05-16 | 2014-08-06 | 北京化工大学 | Functional metal-organic framework based on rare earth metal cluster and preparation method thereof |
CN104865232A (en) * | 2015-05-26 | 2015-08-26 | 天津师范大学 | Method for selectively detecting ascorbic acid by utilizing metal-organic framework material |
CN106810571A (en) * | 2017-02-06 | 2017-06-09 | 辽宁大学 | One kind is based on YIIIRare earth cluster metal-organic framework materials and its preparation method and application |
CN109211859A (en) * | 2018-09-27 | 2019-01-15 | 华南理工大学 | Hydrogel optical fiber based on luminous MOFs and preparation method thereof and sensing device |
CN109810256A (en) * | 2019-01-30 | 2019-05-28 | 江苏理工学院 | A kind of ternary heteronuclear metal organic framework luminescent material and its preparation method and application |
CN110628040A (en) * | 2019-10-16 | 2019-12-31 | 安阳师范学院 | Cd (II) MOF materials based on 5- (4- [1,2,4] triazol-1-phenyl) -1H-tetrazoles |
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2009
- 2009-11-26 CN CN 200910194155 patent/CN101735798B/en not_active Expired - Fee Related
Non-Patent Citations (2)
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DONGWON MIN等: "Terbium-oxalate-pyridinedicarboxylate coordination polymers suggesting the reductive coupling of carbon dioxide (CO2) polymers suggesting the reductive coupling of carbon dioxide (CO2)to oxalate and Tb(2,4-PDC)(H2O)(C2O4)0.5](PDC = pyridinedicarboxylate)", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
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CN103965230A (en) * | 2014-05-16 | 2014-08-06 | 北京化工大学 | Functional metal-organic framework based on rare earth metal cluster and preparation method thereof |
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CN104865232A (en) * | 2015-05-26 | 2015-08-26 | 天津师范大学 | Method for selectively detecting ascorbic acid by utilizing metal-organic framework material |
CN104865232B (en) * | 2015-05-26 | 2017-05-17 | 天津师范大学 | Method for selectively detecting ascorbic acid by utilizing metal-organic framework material |
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