阅读说明：本技术 一种双发射染料包覆的镧系金属有机框架的制备及应用 (Preparation and application of double-emission dye-coated lanthanide metal organic framework ) 是由 宁张磊 冯莉 董成丽 李明凤 高道江 毕剑 于 2019-09-04 设计创作，主要内容包括：本发明涉及一种双发射染料包覆的镧系金属有机框架的制备及应用,S1,选取原料,稀土铽离子和均苯三甲酸；S2,将均苯三甲酸溶解在乙醇中之后进行搅拌；S3,将S2中得到的溶液中加入0.05M Tb(NO<Sub>3</Sub>)<Sub>3</Sub>·6H<Sub>2</Sub>O水溶液搅拌；S4,静置,离心收集白色沉淀,洗涤之后进行烘干得到白色样品；S5,将样品浸泡在不同浓度的染料中进行处理；S6,收集步骤S5中淡黄色沉淀,对其进行干燥,得到镧系金属有机框架材料；S7,对得到的镧系金属有机框架材料进行检测。该双发射染料包覆的镧系金属有机框架的制备是用不同浓度的7-二乙胺基-4-甲基香豆素包覆得到的金属有机框架,这样使其能够在不同的pH值、环境小分子、溶剂中更准确的检测Pb<Sup>2+</Sup>的存在。(The invention relates to preparation and application of a double-emission dye-coated lanthanide metal organic framework, S1, selecting raw materials, rare earth terbium ions and trimesic acid; s2, dissolving trimesic acid in ethanol and then stirring; s3, adding 0.05M Tb (NO) into the solution obtained in S2 3 ) 3 ·6H 2 Stirring the O aqueous solution; s4, standing, centrifuging, collecting white precipitate, washing, and drying to obtain a white sample; s5, soaking the sample in dyes with different concentrations for treatment; s6, collecting the light yellow precipitate in the step S5, and drying the light yellow precipitate to obtain a lanthanide metal organic framework material; and S7, detecting the obtained lanthanide metal organic framework material. The lanthanide metal organic framework coated by the dual-emission dye is prepared by using 7-diethylamino-4-methyl with different concentrationsThe metal organic framework obtained by coating coumarin enables the metal organic framework to detect Pb more accurately in different pH values, small molecules in environment and solvents 2+ Is present.)

1. Preparation and application of a double-emission dye-coated lanthanide metal organic framework are characterized in that: the method comprises the following operation steps:

s1, selecting raw materials, rare earth terbium ions and trimesic acid;

s2, dissolving trimesic acid in ethanol and then stirring;

s3, adding 0.05M Tb (NO) into the solution obtained in S2₃)₃·6H₂Stirring the O aqueous solution;

s4, standing, centrifuging, collecting white precipitate, washing, and drying to obtain a white sample;

s5, soaking the sample in dyes with different concentrations for treatment;

s6, collecting the light yellow precipitate in the step S5, and drying the light yellow precipitate to obtain a lanthanide metal organic framework material;

and S7, detecting the obtained lanthanide metal organic framework material.

2. Preparation and application of the dual emission dye-coated lanthanide metal-organic framework as described in claim 1, characterized in that: the mixture was stirred at room temperature for 30 minutes in both step S2 and step S3.

3. The preparation and use of dual emission dye coated lanthanide metal-organic frameworks as claimed in claim 1, wherein: in the step S4, the standing time is 12 hours, the baking temperature is 70 ℃, and the baking time is 12 hours.

4. The preparation and use of dual emission dye coated lanthanide metal-organic frameworks as claimed in claim 1, wherein: soaking the sample in 1 × 10 in the step S5^-3，1×10^-2mol·L^-1Taking DMF as a solvent in dyes with different concentrations, carrying out ultrasonic treatment for 1h, and standing for 24 h.

5. The preparation and use of dual emission dye coated lanthanide metal-organic frameworks as claimed in claim 1, wherein: the detection is selectivity, anti-interference and sensitivity.

Technical Field

The invention relates to the technical field of machine frame preparation, in particular to preparation and application of a dual-emission dye-coated lanthanide metal organic frame.

Background

Pb2+ is a heavy metal ion with high toxicity, widely exists in daily life, such as automobile exhaust, cigarette, lead-containing paint, cosmetics, industrial waste water and the like, and poses a threat to human health and environment even at low concentration. Diseases related to Pb2+, such as memory loss, irritability, anemia, cardiovascular diseases, developmental disorder, and neo-paralysis. Therefore, exploring a sensitive method to routinely and efficiently detect Pb2+ is of great interest for clinical diagnosis and environmental monitoring. So far. Several analytical instruments have been reported to detect heavy metals. Inductively coupled plasma mass spectrometry (ICP-MS) is currently a powerful technique for Pb2+ detection, but it requires expensive instruments and is not suitable for on-site analysis. Recently, several methods for detecting Pb2+ have been reported, including surface enhanced raman scattering, colorimetry, and fluorescence. Among them, the fluorescence method is attracting attention because of its advantages of high sensitivity, reliability, low cost, good selectivity, etc.

Lanthanide series metal organic frameworks (Ln-MOFs for short) not only have the porosity of MOFs, but also have own optical properties such as high color purity, macroscopic color, long Stokes shift value and long fluorescence lifetime, which are beneficial to the application of the materials on fluorescent probes, but some Ln-MOFs have the problems as fluorescent probes.

Disclosure of Invention

In order to solve the problems, the invention aims to provide preparation and application of a dual-emission dye-coated lanthanide metal organic framework.

In order to achieve the purpose, the invention provides the following technical scheme: the preparation and application of the double-emission dye-coated lanthanide metal organic framework comprise the following steps:

the method comprises the following steps:

s1, selecting raw materials, rare earth terbium ions and trimesic acid;

s2, the pyromellitic acid is dissolved in ethanol and stirred. (ii) a

S3, adding 0.05M Tb (NO) into the solution obtained in S2₃)₃·6H ₂0, stirring the aqueous solution;

s4, standing, centrifuging, collecting white precipitate, washing, and drying to obtain a white sample;

s5, soaking the sample in dyes with different concentrations for treatment;

s6, collecting the light yellow precipitate in the step S5, and drying the light yellow precipitate to obtain a lanthanide metal organic framework material;

and S7, detecting the obtained lanthanide metal organic framework material.

Preferably, the stirring in steps S2 and S3 is performed at room temperature for 30 minutes.

Preferably, the standing time in the step S4 is 12 hours, and the baking temperature is 70 ℃ for 12 hours.

Preferably, in the step S5, the sample is soaked in dyes with different concentrations of 1 × 10-3, 1 × 10-2mo/L, DMF is used as a solvent, ultrasonic treatment is carried out for 1h, and the sample is placed for 24 h.

Preferably, the detection is selectivity, interference resistance and sensitivity.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, a lanthanide metal organic framework is formed by taking terbium rare earth ion (Tb3+) which is one of the most important fluorescent activators and trimesic acid (TMA) which has a symmetrical structure and multiple coordination points as raw materials, and the lanthanide metal organic framework coated by the double-emitting dye is coated by 7-diethylamino-4-methylcoumarin with different concentrations, so that the presence of Pb2+ can be better detected in different PU values, environmental micromolecules, solvents and instruments.

Drawings

FIG. 1 is a schematic diagram of the synthesis of dual emission Dye-coated lanthanide metal-organic frameworks (Dye @ Tb-MOFs) according to the present invention;

FIG. 2 is an XRD spectrum of a lanthanide metal organic frameworks (Tb-MOFs) material and a Dye-coated lanthanide metal organic frameworks (Dye @ Tb-MOFs) and a simulated La (TMA) (H2O)6 single crystal in accordance with the present invention;

FIG. 3 is a thermogravimetric analysis of Tb-MOFs and Dye @ Tb-MOFs in the present invention;

FIG. 4 is an excitation spectrum and an emission spectrum of Tb-MOFs (a) and dye (dye) (b) in the present invention;

FIG. 5 is an excitation spectrum of Dye @ Tb-MOFs of the present invention;

FIG. 6 is a graph showing the emission spectra of Dye @ Tb-MOFs of different Dye concentrations in the present invention;

FIG. 7 is a graph (a) showing the emission spectra of dyes at different concentrations and a linear relationship (b) between the fluorescence intensity and the dye concentration in accordance with the present invention;

FIG. 8 is an emission spectrum (a) and CIE chromaticity diagram (b) of Dye @ Tb-MOFs of the present invention at different excitation wavelengths; c is a graph of the change in fluorescence intensity at 459nm and 544nm at different excitation wavelengths for Dye @ Tb-MOFs; d is the correlation of I459nm/I544nm with the excitation wavelength;

FIG. 9 is a graph showing the emission spectra of Dye @ Tb-MOFs of the present invention in aqueous solutions of different metal ions at a concentration of 10-2M.

FIG. 10 is a graph showing the relationship between the changes in values of I459nm/I544nm in aqueous solutions of different metal ions having a concentration of 10-2M in accordance with the present invention (a) and the changes in fluorescence intensity in the presence of Pb2+ and other interfering metal ions in Dye @ Tb-MOFs (b);

FIG. 11 is a graph (a) showing the emission spectra of Dye @ Tb-MOFs in accordance with the change in the concentration of Pb2+ and a relationship (b) between I459nm/I544nm and the concentration of Pb2 +;

FIG. 12 is a block diagram of the steps of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.