CN104151366B - A kind of 3d-4f heterometallocenes-organic framework materials and preparation method thereof - Google Patents
A kind of 3d-4f heterometallocenes-organic framework materials and preparation method thereof Download PDFInfo
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Abstract
A kind of 3d-4f heterometallocenes-organic framework materials, its chemical formula is { [Zn3Tb2(TTHA)2(H2O)6]·10H2O}n；Described metal framework structure exists the Tb ion of a kind of coordination environment and the Zn ion of two kinds of coordination environments, Tb, Zn1、Zn2Constituting a trimerization unit, trimerization unit connects into a 2D plane by continuous symmetry, and 2D plane defines a three-dimensional net structure presenting cellular pore passage structure in c-axis direction by the connection function of part；Its preparation method is with zinc nitrate hexahydrate and six nitric hydrate terbiums as slaine, with H6TTHA is part, with H2O is solvent, and mixed solution is agitated, bake, separate and wash solid prepares.The invention have the advantage that this metal-organic framework materials raw material is easy to get, crystallization purity is high；Novel structure, acid-fast alkali-proof；Carcinogenic organic solvent benzene series thing had good fluorescence identifying effect.
Description
Technical field
The present invention relates to the preparation of porous crystalline material, particularly a kind of 3d-4f heterometallocenes-organic framework materials and preparation method thereof.
Background technology
Metal-organic framework (Metal-Organic
Frameworks, MOFs) material be by metal ion or bunch and organic ligand between a kind of porous crystalline material formed by coordinate bond effect, it not only has charming topological structure, but also in many-sides such as sensor, magnetic material, gas absorption separation, catalysis, photoelectricity, there is tempting application potential, just developing rapidly and becoming the energy, material and the study hotspot of life science crossing domain.
All the time, compared to pure transition metal and pure rare earth MOFs, the research of 3d-4f heteronuclear MOFs is the most relatively fewer.This is likely due to cause the two to be easy to individually to be coordinated synthesizing the Competition of transition metal and rare earth metal during this kind of MOFs.Finding suitable synthesis condition, the conditions such as temperature, pH value, concentration that regulate make it jointly participate in being coordinated the striving direction being always devoted to heteronuclear MOFs researcher.Rare earth element has good photoluminescent property, especially Eu, Tb, and its rare earth MOFs material built can realize the identification to specific zwitterion and organic molecule, there is huge application potential in terms of fluorescence probe and molecule sensor.In rare earth compound, add transition metal can improve the photoluminescent property of rare earth compound, because transition metal ions has less ligancy, that can reduce around rare earth ion in 3d-4f heterocaryotizes compound is sterically hindered, stop rare earth ion to be coordinated with solvent molecule, and then can reach to strengthen the purpose of fluorescence intensity.Therefore, using transition-rare earth metal to build metal-organic framework, can obtain the MOFs that fluorescence property is excellent, this is also one of its reason becoming current Coordinative Chemistry area research focus.
Mononuclear aromatic all has toxicity, and wherein benzene is carcinogenic substance, and other benzene homologues the most all have toxicity in various degree to human body and aquatile.Therefore, benzene, toluene, paraxylene, meta-xylene, ortho-xylene have been listed in China's pollutant blacklist, so the monitoring meaning carrying out benzene homologues is the most great.2007 Nian Chenbang woods seminars report the first rare earth metal MOF, i.e. Eu (the BTC) (BTC to organic molecule with fluorescence identifying effect
=1,3,5-benzenetricarboxylic acids), this MOF has obvious recognition reaction to organic molecule DMF and acetone molecules.But for there being the hazardous solvents such as the benzene and toluene of carcinogenesis to have the MOFs material of recognition reaction but to report seldom, especially 3d-4f heteronuclear MOFs.Therefore design to synthesize to have and identify that the 3d-4f heteronuclear MOFs material of the benzene series carcinogen such as benzene, toluene has great Research Significance.
Summary of the invention
It is an object of the invention to for the above-mentioned state of the art and existing problems, a kind of 3d-4f metal-organic framework materials and preparation method thereof is provided, this compound all has preferable stability to acid, alkali, has the function of fluorescence identifying to benzene homologues, can be applicable to industrialized production.
Technical scheme:
A kind of 3d-4f heterometallocenes-organic framework materials, chemical formula is { [Zn3Tb2(TTHA)2(H2O)6]·10H2O}n, in formula: n is 1 to the most infinite natural number；TTHA is 1,3,5-triazine-2,4,6-three hexaacetic acid；There is the Tb and the Zn of two kinds of coordination environments of a kind of coordination environment in described metal framework structure elementary cell, wherein Tb is ten coordinations, is coordinated from different TTHA part carboxyl oxygens with four respectively, Zn1And Zn2All take the octahedral coordination pattern of deformation；To Zn1For, four oxygen atoms from two TTHA parts take identical coordination mode to occupy octahedral plan-position, and axial location is occupied by two hydrones, Zn2Also being to be occupied axial location by two hydrones, plan-position is occupied by four oxygen atoms from four different TTHA parts；Part TTHA is as a μ14Bridge is connected to four Tb centers, a Zn1Center and four Zn2Center；The chelating bridging pattern that carboxyl is taked is connected Tb, Zn with single bridging oxygen connection mode1、Zn2Becoming a trimerization unit, trimerization unit connects into a 2D plane by continuous symmetry, and 2D plane defines a three-dimensional net structure presenting cellular pore passage structure in c-axis direction by the connection function of part；Described metal-organic framework belongs to monoclinic system,C2/mSpace group, cell parameter is: a=17.4605 (6), b=17.8792 (5), c=10.7189 (3)
, α=90 °, β=125.466 (2) °, γ=
90°。
The preparation method of a kind of described 3d-4f heterometallocenes-organic framework materials, with six nitric hydrate terbiums as slaine, with H6TTHA is part, and with H2O as solvent, synthesis step is as follows:
1) by Zn (NO3)2·6H2O、Tb(NO3)3·6H2O and H6The mixture of TTHA is put in the polytetrafluoroethylliner liner of hydrothermal reaction kettle, is subsequently adding H2O, stirs 10 min, obtains mixed solution under normal temperature；
2) by the NaOH solution of 10wt%, the pH value of above-mentioned mixed solution is adjusted to 5.5；
3) reactor that will be equipped with above-mentioned mixed solution is put in baking oven, bakes 72h at 150 DEG C, is separated by solid after taking out product；
4) H is used2Above-mentioned solid is washed 3-5 time by O, can be prepared by colourless web crystal 3d-4f heterometallocenes-organic framework materials.
Zn (NO in described mixture3)2·6H2O、Tb(NO3)3·6H2O and H6The mol ratio of TTHA is 5:1:1；Mixture and H2The amount ratio of O is 241mg:10mL.
The application of a kind of described 3d-4f heterometallocenes-organic framework materials, is used for the fluorescence identifying of benzene homologues organic molecule as fluorescence probe.
The invention have the advantage that
1) synthesis material is cheap and easy to get, solvent for use environmental protection, can obtain single crystal form, highly purified crystalline material in building-up process；2) this product structure is novel, has the superperformance of acid-fast alkali-proof；3) this product has the function of fluorescence identifying to organic molecule, and the benzene homologues especially with carcinogenesis has obvious fluorescent quenching function to it, and compared with traditional gas chromatography, the method has the qualitative advantage such as quick, economic, easy.
[accompanying drawing explanation]
Fig. 1 is the single crystal diffraction structure chart of this 3d-4f heterometallocenes-organic framework materials, wherein: Fig. 1 a is that Fig. 1 b is the three-dimensional net structure figure along c-axis direction by the trimerization unit part-structure figure to weighing up.
Fig. 2 is the stability test figure of this 3d-4f heterometallocenes-organic framework materials, is immersed in the aqueous solution of pH=2.5 the powder diagram after a week including compound and compound is immersed in the aqueous solution of pH=12 the powder diagram after a week.
Fig. 3 is this 3d-4f heterometallocenes-organic framework materials fluorescence intensity change relationship experiments figure in selected organic molecule solvent, wherein: Fig. 3 (a) is material fluorescence spectrum figure in different organic molecule solvents, Fig. 3 (b) is the Strength Changes block diagram in material fluorescence spectrum in different organic molecule solvents at maximum absorption wavelength 544nm.
Fig. 4 is the fluorescence intensity change figure dripping micro-benzene in the propyl alcohol that fluorescence intensity is the strongest.
Fig. 5 is the powder diagram after this 3d-4f heterometallocenes-organic framework materials soaks a week in selected organic molecule.
[detailed description of the invention]
Embodiment:
A kind of 3d-4f heterometallocenes-organic framework materials, chemical formula is { [Zn3Tb2(TTHA)2(H2O)6]·10H2O}n, in formula: n is 1 to the most infinite natural number；TTHA is 1,3,5-triazine-2,4,6-three hexaacetic acid；There is the Tb and the Zn of two kinds of coordination environments of a kind of coordination environment in described metal framework structure elementary cell, wherein Tb is ten coordinations, is coordinated from different TTHA part carboxyl oxygens with four respectively, Zn1And Zn2All take the octahedral coordination pattern of deformation；To Zn1For, four oxygen atoms from two TTHA parts take identical coordination mode to occupy octahedral plan-position, and axial location is occupied by two hydrones, Zn2Also being to be occupied axial location by two hydrones, plan-position is occupied by four oxygen atoms from four different TTHA parts；Part TTHA is as a μ14Bridge is connected to four Tb centers, a Zn1Center and four Zn2Center；The chelating bridging pattern that carboxyl is taked is connected Tb, Zn with single bridging oxygen connection mode1、Zn2Becoming a trimerization unit, trimerization unit connects into a 2D plane by continuous symmetry, and 2D plane defines a three-dimensional net structure presenting cellular pore passage structure in c-axis direction by the connection function of part；Described metal-organic framework belongs to monoclinic system,C2/mSpace group, cell parameter is: a=17.4605 (6), b=17.8792 (5), c=10.7189 (3)
, α=90 °, β=125.466 (2) °, γ=
90°。
The preparation method of described 3d-4f heterometallocenes-organic framework materials, with zinc nitrate hexahydrate and six nitric hydrate terbiums as slaine, with H6TTHA is part, with H2O is solvent, and synthesis step is as follows:
1) by 149
Zn (the NO of mg3)2·6H2Tb (the NO of O, 45mg3)3·6H2The H of O and 47mg6The polytetrafluoroethylliner liner putting into hydrothermal reaction kettle of TTHA mixes, adds the H of 10 mL2O, stirs 10 min, obtains mixed solution under normal temperature；
2) by the NaOH solution of 10wt%, the pH value of above-mentioned mixed solution is adjusted to 5.5；
3) reactor that will be equipped with above-mentioned mixed solution is put in baking oven, bakes 72h at 150 DEG C, is separated by solid after taking out product；
4) H is used2Above-mentioned solid is washed 4 times by O, can be prepared by colourless web crystal 3d-4f heterometallocenes-organic framework materials, is 58% based on the calculated productivity of metal Tb.
3d-4f metal organic frame hybrid material by preparation is used for the fluorescence identifying of organic molecule, method is: the material of preparation is taken respectively 3mg be immersed in 2mL propyl alcohol, water, ethanol, methyl alcohol, acetonitrile, oxolane, acetone, 1,4-dioxane, N, in dinethylformamide, benzene, toluene, ortho-xylene, meta-xylene, paraxylene, ultrasonic oscillation is to suspension, with its characteristic emission peak intensity of fluorescent spectrophotometer assay.
This multi-function metal has-property representation of machine frame material structure:
1) this metal has-a structure determination of machine frame material:
Crystal structure determination uses Supernova type X-ray single crystal diffractometer, uses through graphite monochromatised Mo-KαRay (λ=0.71073) is Incident Irradiation Source, point diffraction is collected with ω-φ scan mode, obtain cell parameter through least square refinement, utilize SHELXL-97 direct method to solve crystal structure from difference Fourier electron-density map, and through Lorentz and polarity effect correction.All of H atom is synthesized by difference Fourier and is determined by ideal position calculating.Solvent molecule quantity accurately is tested by thermogravimetric and elementary analysis and is determined, detailed axonometry data are shown in Table 1.
Table 1: the crystallographic data of complex
| Molecular formula | Zn3Tb2C30N12O40H56 |
| Molecular weight | 1720.84 |
| Temperature/K | 293.0 |
| Crystallographic system | monocline |
| Space group | C2/m |
| Cell parameter | a=17.3862(11) Å |
| b=17.9923(11) Å | |
| c=10.7535(7) Å | |
| α=90.00 | |
| β =125.455(6) ° | |
| γ=90.00° | |
| Volume,3 | 2740.1(3) |
| Repetitive in structure cell | 2 |
| Density (calculating)/ mg mm3 | 1.889 |
| Absorption coefficient/mm-1 | 3.938 |
| Angular range/deg | 2.88 to 25 |
| Based on F2The goodness of fit | 1.097 |
| The final R factor [I > 2 σ (I)] | R1 = 0.0231 |
| The R factor (all data) | R1 = 0.0251 |
Fig. 1 is the single crystal diffraction structure chart of this 3d-4f heterometallocenes-organic framework materials, in formula, n is 1 to the most infinite natural number, show that this material is polymer, wherein: Fig. 1 a is that Fig. 1 b is the three-dimensional net structure figure along c-axis direction by the trimerization unit part-structure figure to weighing up.
2) this metal has-a stability test of machine frame material:
20 mg samples are separately immersed in the water of pH=2.5, pH=12 holding one week, filter, solid ethanol rinse air dries, carries out powder diffraction test.
Fig. 2 is the stability test figure of this 3d-4f heterometallocenes-organic framework materials, it is immersed in the aqueous solution of pH=2.5 powder diagram after a week including compound-material and compound-material soaks in the aqueous solution of pH=12 powder diagram after a week, figure shows: the structure of material can well be kept, illustrate that this material has preferable acid-proof alkaline.
3) photoluminescent property of this frame structure characterizes:
Fig. 3 is this 3d-4f heterometallocenes-organic framework materials fluorescence intensity change relationship experiments figure in selected organic molecule, wherein: Fig. 3 (a) is material fluorescence spectrum figure in different organic molecule solvents, Fig. 3 (b) is the Strength Changes block diagram in material fluorescence spectrum in different organic molecule solvents at maximum absorption wavelength 544nm.As can be seen from Figure 3: this compound-material has obvious fluorescent quenching effect for benzene homologues organic molecule, this is the first 3d-4f heteronuclear MOF material benzene homologues to fluoroscopic examination effect.Fluorescence intensity order for these organic molecules is propyl alcohol > water > ethanol > methyl alcohol > acetonitrile > oxolane > acetone > dioxane > N,N-dimethylformamide > toluene > paraxylene > ortho-xylene > meta-xylene > benzene.
Fig. 4 is the fluorescence intensity change figure dripping micro-benzene in the propyl alcohol that fluorescence intensity is the strongest, as can be seen from Figure 4: when being gradually added into benzene in the propanol solution of this compound, the downward trend that its fluorescence intensity slows down gradually after presenting the soonest along with the increase of benzene amount, and change substantially.Even when the 0.1%(2mL propyl alcohol that amount is propyl alcohol volume adding benzene adds 0.2 μ L benzene) time, its fluorescent quenching rate has reached 12%, when the 3%(2mL propyl alcohol that amount is propyl alcohol volume adding benzene adds 60 μ L benzene) time, its fluorescent quenching rate has reached 80%, again illustrates this compound-material and benzene homologues especially benzene is had good fluorescence identifying function.
Fig. 5 is the powder diagram after this 3d-4f heterometallocenes-organic framework materials soaks a week in selected organic molecule, figure may indicate that this compound-material has preferable acid-fast alkali-proof performance.
Claims (4)
1. 3d-4f heterometallocenes-organic framework materials, it is characterised in that: chemical formula is
{[Zn3Tb2(TTHA)2(H2O)6]·10H2O}n, in formula: n is 1 to the most infinite natural number；H6TTHA is
1,3,5-triazine-2,4,6-three hexaacetic acid；The structure of described 3d-4f heterometallocenes-organic frame is the most single
There is the Tb and the Zn of two kinds of coordination environments of a kind of coordination environment in unit, wherein Tb is ten coordinations, same respectively
Four are coordinated from different TTHA part carboxyl oxygens, Zn1And Zn2All take the octahedral coordination pattern of deformation；
To Zn1For, four oxygen atoms from two TTHA parts take identical coordination mode to occupy octahedral
The plan-position of body, axial location is occupied by two hydrones, Zn2Also it is to be occupied axial position by two hydrones
Putting, plan-position is occupied by four oxygen atoms from four different TTHA parts；Part TTHA conduct
One μ14Bridge is connected to four Tb centers, a Zn1Center and four Zn2Center；The chela that carboxyl is taked
Close bridging pattern and be connected Tb, Zn with single bridging oxygen connection mode1、Zn2Becoming a trimerization unit, trimerization unit leads to
Crossing continuous symmetry and connect into a 2D plane, 2D plane defines one at c by the connection function of part
Direction of principal axis presents the three-dimensional net structure of cellular pore passage structure；Described 3d-4f heterometallocenes-have machine frame
Frame belongs to monoclinic system, C2/m space group, and cell parameter is:B=17.9923 (11)α=90 °, β=125.455 (6) °, γ=90 °.
2. a preparation method for 3d-4f heterometallocenes-organic framework materials as claimed in claim 1, it is special
Levy and be with six nitric hydrate terbiums as slaine, with H6TTHA is part, with H2O as solvent, and synthesis step
Rapid as follows:
1) by Zn (NO3)2·6H2O、Tb(NO3)3·6H2O and H6The mixture of TTHA puts into hydrothermal reaction kettle
Polytetrafluoroethylliner liner in, be subsequently adding H2O, stirs 10min, obtains mixed solution under normal temperature；
2) by the NaOH solution of 10wt%, the pH value of above-mentioned mixed solution is adjusted to 5.5；
3) reactor that will be equipped with above-mentioned mixed solution is put in baking oven, bakes 72h, take out product at 150 DEG C
After by solid separate；
4) H is used2Above-mentioned solid is washed 3-5 time by O, can be prepared by colourless web crystal 3d-4f heterometallocenes
-organic framework materials.
The preparation method of 3d-4f heterometallocenes-organic framework materials, its feature the most according to claim 2
It is: Zn (NO in described mixture3)2·6H2O、Tb(NO3)3·6H2O and H6The mol ratio of TTHA is
5:1:1；Mixture and H2The amount ratio of O is 241mg:10mL.
4. an application for 3d-4f heterometallocenes-organic framework materials as claimed in claim 1, its feature exists
In: the fluorescence identifying of benzene homologues organic molecule it is used for as fluorescence probe.
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| CN106053413B (en) * | 2016-06-13 | 2019-01-18 | 华东师范大学 | A kind of metal organic fluorescence methanol sense film and preparation method thereof |
| CN109142304B (en) * | 2018-09-30 | 2021-01-01 | 武汉大学 | pH visual ratio fluorescence sensor based on bimetallic organic framework and application |
| CN111234254B (en) * | 2020-02-27 | 2021-07-27 | 西北大学 | D-p heteronuclear bimetallic organic framework material capable of realizing white light emission and preparation method thereof |
| CN112915968A (en) * | 2021-01-25 | 2021-06-08 | 肇庆市武大环境技术研究院 | Application of europium-based metal organic framework material as water vapor adsorption material |
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