CN113234435B - Metal organic framework composite material for detecting pesticide nitenpyram and preparation method and application thereof - Google Patents
Metal organic framework composite material for detecting pesticide nitenpyram and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a metal organic framework material capable of being used for detecting the concentration of a pesticide nitenpyram, and a preparation method and application thereof. The fluorescent probe material is rapidly prepared in water under the condition of stirring at room temperature, so compared with the prior art, the fluorescent probe material has the remarkable advantages that: (1) The fluorescent probe has simple preparation process, environmental protection and energy saving; (2) The fluorescent probe material prepared by the process has high purity and strong stability; (3) The fluorescent probe material has a self-correcting function and higher sensitivity; (4) The probe material has magnetic separation performance, and can be quickly recovered through simple magnetic separation; (5) The probe has good recycling performance, and can be recycled for the determination of the nitenpyram through rapid magnetic separation.
Description
Technical Field
The invention relates to a nitenpyram-identified metal organic framework material fluorescent probe, in particular to a metal organic framework composite material which has double-wavelength self-correction and magnetic separation and can be circularly used for nitenpyram detection, and a preparation method and application thereof.
Background
The pesticide plays an important role in promoting the growth of global agricultural production as a chemical agent for preventing and controlling plant diseases and insect pests and regulating plant growth. However, the large-scale use of pesticides exacerbates the pollution of ecosystems, threatening public health and food safety. For example, pesticide accumulation in the food chain is associated with leakage from underground storage tanks or influx of surface water, which may lead to acute or chronic diseases. Therefore, detection of pesticides and their residues becomes especially important. Currently, some large-scale instruments and methods are widely used for detecting the concentration of pesticide residues, such as high performance liquid chromatography, mass spectrometry, gas chromatography and the like. Although these methods have high accuracy, they have some disadvantages, such as complicated sample pretreatment, high analysis cost, and the need for skilled manpower. In contrast, fluorescence detection techniques exhibit many advantages, such as fast response, signal visualization, and simplicity of operation. Most of the currently reported fluorescence sensors rely on the change (such as intensity enhancement or quenching) of a single fluorescence signal, and these fluorescence probes are susceptible to the interference of external environmental factors unrelated to the concentration of the analyte, such as light scattering of a sample matrix, fluctuation of an excitation source, a special microenvironment around the probes, local concentration change of the probes, and the like, which all generate unavoidable interference. The self-correcting fluorescent probe material utilizes the ratio or difference of two fluorescent bands to replace the absolute intensity of one fluorescent band for quantification, and provides the practical advantage of built-in variable correction, thereby having higher signal-to-noise ratio and sensitivity. In addition, compared with homogeneous phase fluorescent probe materials, the heterogeneous phase fluorescent sensing probe materials have the advantages of being separable and recyclable. Therefore, the design and synthesis of heterogeneous fluorescent sensing probe materials for pesticide detection are of great significance.
As a novel crystalline porous material, a metal-organic framework (MOFs) has excellent properties such as high porosity, super-large specific surface area, porosity, order, adjustable pore channel structure and the like, so that the MOFs has excellent performance and application prospects in the aspects of adsorption, separation, catalysis, sensing, ion conduction and the like. At present, a great deal of literature reports that MOFs are used as a carrier to stabilize and disperse guest molecules such as photosensitizers or inorganic nanoparticles to prepare host-guest composite materials, and the MOFs are used in different fields. Up to now, MOFs are widely used as fluorescent probes for detecting metal ions, biological small molecules, organic volatile solvents, etc. Compared with other fluorescent probe materials, the MOFs probe material also has the advantages of adsorption and enrichment, so that the MOFs probe material has higher sensitivity in the aspect of analysis and detection and has lower detection limit. Therefore, MOFs are an ideal carrier for preparing heterogeneous fluorescent probe materials.
Among many MOFs, zeolite imidazole carboxylate framework MOFs (ZIFs) have the characteristics of MOFs and molecular sieves, such as ultra-large specific surface area, high porosity, high crystallinity, abundant functional groups and excellent stability, so that the zeolite imidazole ester framework MOFs has important application values in various fields of catalysis, separation, sensing and the like. In ZIFs, where ZIF-8 is Zn 2+ Is a metal ion, and is characterized in that,the 2-methylimidazole is a ZIF with a sodalite topological structure formed by molecular self-assembly of an organic ligand, and has the advantages of easiness in preparation, permanent porosity, high structural flexibility, strong stability and the like. ZIF-8 is therefore an ideal photosensitizer carrier.
Currently, only a few documents report that luminescent MOFs materials are used to detect the concentration of nitenpyram. Recently, ye et al reported rhodamine B modified zirconium-based MOFs (RhoB @ Zr-MOFs) and used for the assay of nitenpyram (L.Yang, Y.L.Liu, C.G.Liu, Y.Fu, et al.A build-in self-catalysis luminescence sensor based on RhB @ Zr-MOF for detection of locations, nitro applications and therapeutics, RSC adv.,2020,10, 19149). Xing et al prepared eosin-modified zirconium-based MOFs (EY @ Zr-MOFs) for determining nitenpyram concentration (Z.H.Wei, D.S.Chen, Z.F.Guo, et al. Eosin Y-embedded zirconium-based metal-organic framework as a dual-emitting brick-in selected-fibrous platform for pest detection. Inorg.Chem.,2020,59, 5386). Fu et al first prepare Cd-based MOFs material by hydrothermal synthesis, then soak Rho B and Rho6G into the MOFs material frame to prepare Rho B @ Cd-MOFs and Rho6G @ Cd-MOFs, and then use them in nitenpyram concentration determination (L.Yang, Y.L.Liu, C.G.Liu, et al.two luminescence dye @ MOFs system as dual-emitting platform for effective pest determination.J.Hazard.Mater., 2020,381, 120966). According to several reported nitenpyram MOFs probe materials, rhoB @ Zr-MOFs, rho B @ Cd-MOFs and Rho6G @ Cd-MOFs are synthesized by a two-step method, the MOFs material is synthesized by a solvothermal method, and then dye molecules are modified into an MOFs frame by soaking. Therefore, the nitenpyram probe material is complex to synthesize and poor in stability. In addition, EY @ Zr-MOFs in the above documents is synthesized by a one-step method, but is prepared by a hydrothermal synthesis method in an organic solvent DMF, and the reaction time is long. Furthermore, the nitenpyram probe materials reported in the above documents do not have magnetic separation performance, making their recycling difficult. Therefore, the heterogeneous MOFs fluorescent probe material which is rapidly synthesized in environment-friendly solvent water by adopting a one-pot method, has double-wavelength self-correction and magnetic separation functions, and can be circularly used for pesticide nitenpyram detection has important significance.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a rapid, simple, convenient, green and pollution-free MOFs composite probe material preparation process, and the process is used for detecting the concentration of pesticide residue nitenpyram in water. The magnetic metal organic framework material prepared by the method of stirring in the environment-friendly solvent water at room temperature is simple in preparation process, green and environment-friendly, and the synthesized luminescent magnetic MOFs material is high in purity and stability, and has the advantages of being rapid, simple and convenient and high in sensitivity in the detection aspect of nitenpyram.
In order to achieve the experimental purpose, the technical scheme of the invention is as follows: a preparation method of a metal organic framework material with nitenpyram identification detection comprises the following steps:
(1) Preparation of magnetic Fe 3 O 4 A nanoparticle; the magnetic Fe 3 O 4 The nano particles are prepared by adopting a polyvinylpyrrolidone method;
(2) Weighing the product Fe obtained in the step (1) 3 O 4 Adding two fluorescent reagents of rhodamine 6G (Rho 6G) and fluorescent Brightener BBU (BBU) with different emission wavelengths into nanoparticles, adding 2-methylimidazole solution required by synthesis of metal organic framework material, uniformly dispersing by ultrasonic wave, and adding Zn (NO) 3 ) 2 ·6H 2 O, stirring for 10 minutes at room temperature, then performing magnetic separation, washing and drying to obtain the double-wavelength self-correcting metal organic framework BBU/Rho6G @ Fe with nitenpyram recognition detection 3 O 4 @ ZIF-8 composite material; said Fe 3 O 4 The addition amount of (A) is 0.2-1.0mL; the molar ratio of BBU to rhodamine 6G is 1; zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:10～1:35。
preferably, the method comprises the following steps: zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1.
Preferably, magnetic Fe is prepared 3 O 4 A nanoparticle; said magnetic Fe 3 O 4 The preparation method of the nano-particles comprises the following steps: adding FeCl into 80mL of distilled water 2 ·4H 2 O (0.86 g) and FeCl 3 ·6H 2 O(2.36g)， N 2 Protection 5mL of aqueous ammonia (25 wt%) was added dropwise to the above mixture, heated to 80 deg.C, stirred for 1h, washed several times with water, and dispersed in 20mL of water. Then adding 1mL of polyvinylpyrrolidone aqueous solution containing 200mg, stirring at room temperature for 24h, and collecting Fe by magnetic separation after the reaction is finished 3 O 4 The nanoparticles were washed several times with water and then dispersed into 30mL of water for further use.
Preferably, said Fe 3 O 4 The addition amount of (2) is 0.5mL; the molar ratio of BBU to rhodamine 6G is 5.
In order to achieve the above experimental purpose, another technical solution of the present invention is as follows: the metal-organic framework material with nitenpyram recognition detection prepared by any one of the methods.
In order to achieve the above experimental objectives, another technical solution of the present invention is as follows: the application of the metal organic framework material with nitenpyram identification detection has the advantages of magnetic separation, dual-wavelength self-correction and cyclic utilization, and the metal organic framework material can be applied to selective identification of pesticide nitenpyram.
The MOFs fluorescent probe is used for high-selectivity and high-sensitivity identification of nitenpyram in a water body, and can be circularly used for detecting the nitenpyram concentration through simple magnetic separation.
The invention has the beneficial effects that:
compared with the prior art, the invention has the remarkable advantages that:
(1) The nitenpyram magnetic MOFs fluorescent probe material provided by the invention is quickly synthesized in environment-friendly solvent water under the condition of stirring at room temperature. The preparation process does not produce toxic and harmful byproducts, thereby being more environment-friendly. In addition, the material is prepared only by a common reaction vessel and a simple stirring device, so that the preparation process is simple and the cost is low;
(2) The fluorescent probe material prepared by the process has strong stability, and the fluorescence intensity of the fluorescent probe material is stable in water for several days and cannot be attenuated;
(3) The fluorescent probe material belongs to a dual-wavelength self-correcting probe material, and has high sensitivity;
(4) The probe material has magnetic separation performance, can realize quick recovery through simple magnetic separation, can be circularly used for the determination of the nitenpyram, and has excellent cycle performance, but the nitenpyram detection probes reported in the current literature do not have the magnetic separation performance;
(5) The probe material has quick response time to nitenpyram detection;
(6) The probe material has good selectivity when being used for nitenpyram detection, and is not interfered by other common pesticides, inorganic cations, anions and the like.
(7) The BBU/Rho6G @ Fe can be rapidly prepared in water 3 O 4 @ ZIF-8 composite material. At present, the synthesis and preparation of Fe are also reported in the literature 3 O 4 The @ ZIF-8 composite material is usually prepared in methanol, and BBU is insoluble in methanol solvent, so that the one-step preparation of BBU/Rho6G @ Fe cannot be realized in methanol solvent 3 O 4 @ ZIF-8 material. In addition, this application employs BBU/Rho6G @ Fe preparation in water 3 O 4 @ ZIF-8, by continuously debugging Zn (NO) 3 ) 2 ·6H 2 Concentration and ratio of O and 2-methylimidazole, zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1.
(8)Fe 3 O 4 There are many synthetic methods for preparing Fe, and this application has tried various methods to prepare Fe 3 O 4 The method comprises (1) adding FeCl to ethylene glycol 3 Sodium citrate and sodium acetate, dissolving and mixingUniformly transferring the mixture into a high-temperature reaction kettle, and obtaining a black product Fe through a hydrothermal reaction 3 O 4 Cooling to room temperature after the reaction is finished, collecting a product through magnetic separation, washing with pure water and absolute ethyl alcohol respectively, and drying to obtain magnetic Fe 3 O 4 (ii) a (2) Dissolving 2mmol of ferric triacetylacetone in a mixed solvent of 10mL of benzyl ether and 10mL of oleylamine, reacting for 1h at 110 ℃, then heating to 300 ℃ for reacting for 2h, cooling to room temperature, then adding 50mL of ethanol solution, carrying out magnetic separation, washing with ethanol, drying, and then obtaining the magnetic Fe 3 O 4 The nanoparticles were re-diffused into 1.0mL of oleic acid for further use. (3) FeCl 3 ·6H 2 O(75mL，134mmol L -1 ) And FeCl 2 ·4H 2 O (75mL, 67mmol L-1), then NaOH solution (2 mol L) is gradually added dropwise -1 30 mL) and heated to 60 ℃, and the ultrasonic reaction is carried out for 1h, after the reaction is finished, the product is collected through magnetic separation, washed by pure water and absolute ethyl alcohol respectively and dried to obtain magnetic Fe 3 O 4 。
Fe obtained by the above preparation method 3 O 4 It could not be loaded into the ZIF-8 pore channels in the aqueous phase. Fe modified with polyvinylpyrrolidone of the present application 3 O 4 Can be quickly loaded into the ZIF-8 pore channel in the water phase.
The fluorescent probe can detect the residual concentration of the pesticide nitenpyram in the water body through the change of the fluorescence intensity, and the fluorescent probe material is quickly prepared in water under the condition of stirring at room temperature, so compared with the prior art, the fluorescent probe has the remarkable advantages that: (1) The fluorescent probe has simple preparation process, environmental protection and energy saving; (2) The fluorescent probe material prepared by the process has high purity and strong stability; (3) The fluorescent probe material has a self-correcting function and higher sensitivity; (4) The probe material has magnetic separation performance, and can be quickly recovered through simple magnetic separation; (5) The probe has good recycling performance, and can be recycled for the determination of nitenpyram through rapid magnetic separation; (6) In the aspect of the detection of the nitenpyram, the fluorescent probe has the advantages of strong stability, high sensitivity and short response time. Therefore, the pesticide nitenpyram fluorescent probe provided by the invention has obvious advantages in the aspects of preparation method and nitenpyram concentration detection.
Drawings
In order to facilitate further understanding of the present application, some of the illustrative drawings are provided herein and are not to be construed as unduly limiting the present application.
FIG. 1 is a ZIF-8 crystal structure of the present invention;
FIG. 2 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 A schematic of the preparation of @ ZIF-8;
FIG. 3 is BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 @ZIF-8、Fe 3 O 4 Synthetic ZIF-8, simulated ZIF-8 powder X-ray diffraction patterns;
FIG. 4 is ZIF-8 and BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 pictures under visible light;
FIG. 5 shows Fe in the present invention 3 O 4 Scanning electron microscope images of;
FIG. 6 shows BBU/Rho6G @ Fe of the present invention 3 O 4 @ ZIF-8-1 scanning electron microscopy and transmission electron microscopy;
FIG. 7 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 @ ZIF-8-1 and Fe 3 O 4 Hysteresis loop curve of (1);
FIG. 8 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 The @ ZIF-8-1 is schematically shown under the action of an external magnetic field;
FIG. 9 shows aqueous solutions of BBU and Rho6G, as well as ZIF-8, BBU/Rho6G @ Fe 3 O 4 @ ZIF-8 and Fe 3 O 4 Absorption spectrum of solid powder sample;
FIG. 10 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 The three-dimensional fluorescence spectrum of @ ZIF-8-1;
FIG. 11 is an absorption spectrum of nitenpyram;
FIG. 12 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 The photostability map of @ ZIF-8-1;
FIG. 13 shows a fluorescent probe material according to the present inventionBBU/Rho6G @ Fe material 3 O 4 @ ZIF-8-1 changes along with the increase of the concentration of nitenpyram in a fluorescence spectrogram;
FIG. 14 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 @ ZIF-8-2 changes along with the increase of the concentration of nitenpyram in a fluorescence spectrogram;
FIG. 15 is BBU/Rho6G @ Fe in the present invention 3 O 4 A graph showing the time-dependent change of the @ ZIF-8-1 fluorescent probe material after being added with nitenpyram;
FIG. 16 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 A response graph of the @ ZIF-8-1 fluorescent probe material to an interferent, wherein the concentration of nitenpyram is 8.0 mu M, and the concentration of other interferent is 80.0 mu M;
FIG. 17 fluorescent probe material BBU/Rho6G @ Fe of the present invention 3 O 4 The @ ZIF-8-1 fluorescent probe material is used for selectively detecting the nitenpyram in the presence of other interfering substances, wherein the concentration of the nitenpyram is 8.0 mu M, and the concentration of the other interfering substances is 80.0 mu M;
FIG. 18 shows BBU/Rho6G @ Fe as fluorescent probe material of the present invention 3 O 4 And @ ZIF-8-1 has recycling performance in nitenpyram detection.
Detailed Description
The contents of the present invention will be further clarified by the following examples, which are not intended to limit the scope of the present invention, and various modifications that can be made by those skilled in the art without inventive efforts based on the technical solution of the present invention are still within the scope of the present invention.
Example 1.Fe 3 O 4 Synthesis of (2)
80mL of distilled water was added with FeCl 2 ·4H 2 O (0.86 g) and FeCl 3 ·6H 2 O(2.36g)，N 2 To the mixture was added dropwise 5mL of aqueous ammonia (25 wt%), heated to 80 deg.C, stirred for 1h, washed with water several times, and dispersed in 20mL of water. Then adding 1mL of polyvinylpyrrolidone aqueous solution containing 200mg, stirring at room temperature for 24h, and collecting Fe by magnetic separation after the reaction is finished 3 O 4 The nanoparticles were washed several times with water and then dispersed in 30mL of water for further processingThe application is as follows. The morphology structure of the material is observed by a Scanning Electron Microscope (SEM) and a transmission electron microscope, and the result shows that the material is a uniform spherical result and is uniformly dispersed as shown in figure 6. The magnetic property of the magnetic material is studied by hysteresis curves, as shown in FIG. 7, and the experiment shows that the prepared Fe 3 O 4 Has strong magnetism.
Example 2 BBU/Rho6G @ Fe 3 O 4 Synthesis of @ ZIF-8-1
Firstly, 0.01mol/L BBU and 0.01 mol/L10 mL rhodamine 6G aqueous solution are prepared. Transferring 1.0mL of 0.01mol/L BBU, 0.2mL of 0.01mol/L rhodamine 6G and 0.5mL of Fe prepared above 3 O 4 Magnetic ions are fully and uniformly mixed. 30mmol of 2-methylimidazole was then weighed, and 3.0mL of H was added 2 And (4) carrying out ultrasonic dissolution on O, adding the O into the mixed solution, and uniformly stirring. Weighing 1mmol Zn (NO) 3 ) 2 ·6H 2 O dissolved in 1mL H 2 O, dropwise adding it to the above solution, and adding Zn (NO) 3 ) 2 ·6H 2 O is generated with a large amount of precipitate immediately, then stirring at room temperature for 10 min to stop reaction, magnetically separating, washing with water and ethanol until the supernatant is almost colorless, and drying to obtain BBU/Rho6G @ Fe 3 O 4 @ZIF-8-1。
Example 3 BBU/Rho6G @ Fe 3 O 4 Synthesis of @ ZIF-8-2
0.1mL of 0.01mol/L BBU, 1.0mL of 0.01mol/L rhodamine 6G and 0.5mL of Fe prepared above are transferred 3 O 4 Magnetic ions are fully and uniformly mixed. 30mmol of 2-methylimidazole was then weighed, and 3.0mL of H was added 2 And (4) carrying out ultrasonic dissolution on O, adding the O into the mixed solution, and uniformly stirring. Weighing 1mmol Zn (NO) 3 ) 2 ·6H 2 O dissolved in 1mL H 2 O, adding it dropwise to the above solution, and adding Zn (NO) 3 ) 2 ·6H 2 O is generated with a large amount of precipitate immediately, then stirring at room temperature for 10 min to stop reaction, magnetically separating, washing with water and ethanol until the supernatant is almost colorless, and drying to obtain BBU/Rho6G @ Fe 3 O 4 @ZIF-8-2。
Example 4 BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 and BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-2 knotCharacterization of structure and Properties
Study of BBU/Rho6G @ Fe by powder X-ray (PXRD) 3 O 4 @ ZIF-8-1 and BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-2 (including BBU/Rho6G @ Fe) 3 O 4 @ ZIF-8-1 and BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-2), the results are shown in FIG. 3. As can be seen from FIG. 3, ZIF-8 and BBU/Rho6G @ Fe prepared by the present invention 3 O 4 @ ZIF-8 is completely consistent with a theoretical simulated ZIF-8 PXRD spectrogram, which indicates that the BBU/Rho6G @ Fe is successfully prepared 3 O 4 @ ZIF-8, and BBU, rho6G and Fe 3 O 4 The crystal structure integrity of ZIF-8 is not destroyed after loading. BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 as an example, using SEM for BBU/Rho6G @ Fe 3 O 4 The microstructure of @ ZIF-8-1 was characterized and the results are shown in FIG. 6. As can be seen from FIG. 6, BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 exhibits a uniform spheroidal morphology. Magnetic properties of the prepared BBU/Rho6G @ Fe are researched by hysteresis curves, as shown in FIGS. 7 and 8, experiments show that the prepared BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 has excellent magnetic separation performance, and can realize magnetic separation under the action of an external magnetic field for 1 minute.
BBU, rho6G aqueous solution, ZIF-8, BBU/Rho6G @ Fe 3 O 4 @ ZIF-8 and Fe 3 O 4 The absorption spectrum of the solid powder sample is shown in FIG. 9. As can be seen from the figure, ZIF-8 has no absorption band in the range of 300-700 nm. By comparing with BBU and Rho6G water solution absorption spectra, it can be seen that BBU/RhoB @ Fe loaded with BBU and Rho6G 3 O 4 The absorption band of @ ZIF-8 is derived from BBU and RhoB, which also indicates that BBU and RhoB were successfully loaded into the ZIF-8 channels.
Research of BBU/Rho6G @ Fe through three-dimensional fluorescence spectroscopy 3 O 4 Luminous property of @ ZIF-8-1. As can be seen from FIG. 10, BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 has two emission bands, one at 433nm, which is derived from the emission of the fluorescent whitening agent BBU, and the other at 550nm, which is derived from the emission of rhodamine 6G. Ultraviolet lamp continuously irradiating BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1, then byThe stability of the composite material is researched through the change of the luminescence spectrum, and the result is shown in FIG. 12, which shows that the composite material has strong light stability, and the luminescence intensity is still stable after continuous illumination for 80 minutes. Furthermore, BBU/Rho6G @ Fe can be seen from the three-dimensional fluorescence spectrum 3 O 4 @ ZIF-8-1 has an excitation band at 360nm which coincidently overlaps with the absorption spectrum of nitenpyram (as shown in FIG. 11), which lays a foundation for the detection of the nitenpyram concentration.
Example 5 application
The invention provides BBU/Rho6G @ Fe 3 O 4 The application of the @ ZIF-8 magnetic nano composite material in the aspect of pesticide detection: BBU/Rho6G @ Fe 3 O 4 @ ZIF-8 is dispersed in ethanol, ultrasonic diffusion is uniform, and then 365nm is used as an excitation wavelength to detect the concentration of the pesticide nitenpyram through fluorescence emission spectrum change. After each detection, the nitenpyram can be detected through magnetic separation and ethanol washing circulation.
The specific application method is as follows: weighing 6mg BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 and BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-2 composite material, dispersing in 3mL ethanol by ultrasonic, after dispersing evenly, then adding nitenpyram with different quantities in turn, and then determining the change of emission spectrum by taking 365nm as the excitation wavelength. As shown in fig. 13 and 14, as the amount of nitenpyram increases, the two emission bands of BBU and rhodamine 6G gradually decrease, and the decrease amplitudes of the two emission bands are different. The relative intensity of two peak intensities of BBU and rhodamine 6G is adopted as a vertical coordinate (i.e. I) 430 /I 550 ) The concentration of nitenpyram is plotted on the abscissa, I 430 /I 550 The probe material has a good linear relation with the concentration of the nitenpyram, which shows that the probe material has a self-correcting function and can be used for detecting the concentration of the nitenpyram. In addition, the detection limits of the nitenpyram are respectively 0.21 and 0.67 mu M according to the linear regression equation, which indicates that the fluorescent probe has high sensitivity.
With BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 is an example to study the response time of titrating nitenpyram. The specific experimental operations were as follows: 6.0mg BBU/Rho6G @ Fe was weighed 3 O 4 @ ZIF-8-1 ultrasonic diffusion into 3mL ethanol, adding 8.0 μM nitenpyram, then immediately testing the emission spectrum change, measuring once every 30s, and the experimental result is shown in FIG. 15, BBU/Rho6G @ Fe 3 O 4 The response time of detecting nitenpyram by @ ZIF-8-1 is about 2 minutes, which shows that the probe material has quick response when being used for detecting nitenpyram and has higher practical application value.
BBU/Rho6G@Fe 3 O 4 @ ZIF-8-1 selectivity test. The specific experimental operations were as follows: 6.0mg BBU/Rho6G @ Fe was weighed 3 O 4 @ ZIF-8-1 ultrasonic diffusion into 3mL ethanol, and multiple portions of BBU/Rho6G @ Fe were prepared by the same experimental operation 3 O 4 @ ZIF-8-1 ethanol diffusion liquid, measuring emission spectrum without adding interfering ions, measuring emission spectrum after adding 80.0 mu M interfering ions, and researching BBU/Rho6G @ Fe through change conditions before and after the emission spectrum 3 O 4 @ ZIF-8-1 Selectivity, results are shown in FIG. 16. Common cations, anions and pesticides do not cause BBU/Rho6G @ Fe 3 O 4 The emission spectrum of @ ZIF-8-1 is obviously changed, and the addition of nitenpyram with one tenth of interfering ion concentration can cause the luminous intensity to be obviously changed. In addition, in the case of a large amount of interfering substances, the probe can still selectively detect the concentration of the nitenpyram (figure 17). The fluorescent probe composite material prepared by the invention has strong nitenpyram selective recognition capability.
BBU/Rho6G@Fe 3 O 4 And @ ZIF-8-1 magnetic separation and recycling test. The specific experimental operations were as follows: 6.0mg BBU/Rho6G @ Fe was weighed 3 O 4 @ ZIF-8-1 is ultrasonically diffused into 3mL of ethanol, an emission spectrum is determined by adopting 365nm excitation, the emission spectrum is determined after 8.0 mu M of nitenpyram is added, the nitenpyram is quickly separated and washed by ethanol for multiple times after the test is finished, then the emission spectrum is determined, the emission spectrum is determined after 8.0 mu M of nitenpyram is added, the emission spectrum is determined, the circulation is repeated, the recycling performance is researched by changing the emission intensity of BBU by an example, and the result is shown in FIG. 18. Experimental results show that BBU/Rho6G @ Fe is added after nitenpyram is added 3 O 4 @ ZIF-8-1 fluorescence quenching, fluorescence recovery after magnetic separation and washing, and no influence on BB after 5 times of such circulationU/Rho6G@Fe 3 O 4 The luminescent property of @ ZIF-8-1, thus illustrating the BBU/Rho6G @ Fe prepared by the invention 3 O 4 @ ZIF-8-1 has excellent recycling properties.
Example 6BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 for detecting concentration of nitenpyram in actual water sample
Taking a flat-topped mountain white tortoise-mountain reservoir as a sampling point, taking water from five places at random, then uniformly mixing, dividing into 3 parts, and numbering 1-3. Separately, 2.0. Mu.M, 6.0. Mu.M and 10.0. Mu.M of nitenpyram were added to 3 water samples by a standard addition method, and then the nitenpyram concentration was measured, three times per sample, an average value was taken, and the recovery rate and the relative standard deviation were calculated, and the results are shown in Table 1. From Table 1 it can be seen that the recovery of nitenpyram is from 99.5% to 104.0%, which indicates BBU/Rho6G @ Fe 3 O 4 @ ZIF-8-1 has good detection effect in an actual water sample.
TABLE 1 BBU/Rho6G @ Fe 3 O 4 Application of @ ZIF-8-1 in detection result of actual water sample
Comparative example 1
The present application has tried various methods to prepare Fe 3 O 4 The method comprises (1) adding FeCl to ethylene glycol 3 Sodium citrate and sodium acetate, dissolving and mixing uniformly, transferring the mixture into a high-temperature reaction kettle, and obtaining a black product Fe through hydrothermal reaction 3 O 4 Cooling to room temperature after the reaction is finished, collecting a product through magnetic separation, washing with pure water and absolute ethyl alcohol respectively, and drying to obtain magnetic Fe 3 O 4 (ii) a (2) Dissolving 2mmol of ferric triacetylacetone in a mixed solvent of 10mL of benzyl ether and 10mL of oleylamine, reacting for 1h at 110 ℃, then heating to 300 ℃ for reacting for 2h, cooling to room temperature, then adding 50mL of ethanol solution, carrying out magnetic separation, washing with ethanol, drying, and then obtaining the magnetic Fe 3 O 4 The nanoparticles were re-diffused into 1.0mL of oleic acid for further use. (3) FeCl is added 3 ·6H 2 O(75mL，134mmol L -1 ) And FeCl 2 ·4H 2 O (75mL, 67mmol L-1), then NaOH solution (2 mol L) is gradually added dropwise -1 30 mL) is heated to 60 ℃, ultrasonic reaction is carried out for 1h, products are collected through magnetic separation after the reaction is finished, and the products are respectively washed and dried by pure water and absolute ethyl alcohol to obtain magnetic Fe 3 O 4 . Fe obtained by the above preparation method 3 O 4 It could not be loaded into the ZIF-8 pore channels in the aqueous phase.
Comparative example 2
So far, only four MOFs fluorescent probe materials for detecting the concentration of nitenpyram are reported. For example, fu and the like firstly prepare Cd-based MOFs by a solvothermal synthesis method, then introduce a luminescent material rhodamine B or rhodamine 6G into a Gd-based MOFs frame by a solution impregnation method to prepare the single-emission-band Rho B @1 and Rho6G @1 composite probe materials, and the probe materials can be used for detecting the concentration of nitenpyram, and the detection limits are 0.48nM and 3nM respectively. The defects that the probe materials are complex to synthesize and need to be completed in multiple steps, and fluorescent molecules in the composite materials obtained by the dipping method easily overflow from MOFs, so that the stability of the composite materials is poor. In addition, the probe does not have a dual-wavelength self-calibration function and is easily interfered by external environment factors (L.Yang, Y.L.Liu, C.G.Liu, et al.Two luminescence dye @ MOFs systems as dual-emitting devices for electronic sensing devices detection. J.Hazard.Mater.,2020,381, 120966).
Xing and the like wrap an eosin dye in a Zr-MOFs framework by a one-pot solvent thermal synthesis method to obtain a probe material EY @ DUT-52 with double emission bands for self-correction and used for detecting nitenpyram, wherein the detection limits are 0.94 mu M and 0.18 mu M. However, such probe materials are synthesized by a solvothermal method, and take a long time, and they require a temperature of 100 ℃ for 72 hours to complete (Z.H.Wei, D.S.Chen, Z.F. Guo, et al.Eosin Y-embedded zirconia-based metal-organic framework as a dual-emitting brick-in selected-fibrous platform for polypeptide detection. Inorg. Chem.,2020,59, 5386).
Yang et al use porphyrin as a connecting ligand, zr as a metal node, and adopt a solvothermal synthesis method to prepare a MOFs material (FMOF) which can be used for detecting nitenpyram and has the detection limit of 0.03 mu g/mL, but the probe material is of a single-wavelength quenching type and has no self-correcting function (Yang, Y.L.Liu, C.G.Liu, et al.two luminescence dye @ MOFs system as dual-emitting platform for expressing the characteristics of pesticides detection. J.Hazard.Mater.,2020,381, 120966).
Ye et al prepared a RhB @ Zr-MOF composite probe material by coating dye molecule rhodamine B in Zr-MOFs by a one-pot solvothermal method, the detection limit of which is 0.2 μ M, although the probe is synthesized in one step, the probe needs to be completed at a high temperature of 120 ℃ for 96h, and the energy consumption is large and the time consumption is long (Yang L., liu Y.L., liu C.G., et al. A build-in self-catalysis luminescence sensor based on RhB @ Zr-MOF for detection of sites, nitro experiments and peptides, RSC adv, 2020,10, 19149).
In summary, the nitenpyram MOFs fluorescent probe material is prepared in an organic solvent in a high-temperature high-pressure reaction kettle so far, so that the energy consumption is large, the time consumption is long, and the magnetic separation and recovery performance is not provided.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the claims of the invention.
Claims (6)
1. A preparation method of a metal organic framework material for nitenpyram identification detection is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of magnetic Fe 3 O 4 A nanoparticle; the magnetic Fe 3 O 4 The nano particles are prepared by adopting a polyvinylpyrrolidone method; preparation of magnetic Fe 3 O 4 The nanoparticle approach is as follows: the magnetic Fe 3 O 4 The preparation method of the nano-particles comprises the following steps: 80mL of distilled water was added with 0.86g of FeCl 2 ·4H 2 O and 2.36 g FeCl 3 ·6H 2 O ，N 2 Dropwise adding 5mL of 25wt% ammonia water into the mixture under protection, heating to 80 ℃, stirring for 1h, washing with water for multiple times, and dispersing in 20mL of water; then 1m was addedL contains 200mg of polyvinylpyrrolidone aqueous solution, stirring for 24h at room temperature, and collecting Fe by magnetic separation after the reaction is finished 3 O 4 The nanoparticles, washed many times with water, then dispersed into 30mL of water for further use;
(2) Weighing the product Fe obtained in the step (1) 3 O 4 Adding two fluorescent reagents rhodamine 6G (Rho 6G) and fluorescent brightener BBU with different emission wavelengths and 2-methylimidazole solution required for synthesizing a metal organic framework material into nanoparticles, uniformly dispersing by ultrasonic, and adding Zn (NO) 3 ) 2 ·6H 2 O, stirring for 10-15 minutes at room temperature, then performing magnetic separation, washing and drying to obtain the dual-wavelength self-correcting metal organic framework BBU/Rho6G @ Fe for nitenpyram recognition and detection 3 O 4 @ ZIF-8 composite; said Fe 3 O 4 The addition amount of (A) is 0.2-1.0mL; the molar ratio of BBU to rhodamine 6G is 1; zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1.
2. The preparation method of the metal-organic framework material for nitenpyram identification and detection according to claim 1, characterized by comprising the following steps: the method comprises the following steps: zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1.
3. The preparation method of the metal-organic framework material for nitenpyram identification and detection according to claim 1, characterized by comprising the following steps: said Fe 3 O 4 The addition amount of (A) is 0.5mL; the molar ratio of BBU to rhodamine 6G is 5 or 1.
4. A metal organic framework material for nitenpyram recognition detection prepared according to the method of any one of claims 1-3.
5. The use of the metal-organic framework material for nitenpyram recognition detection according to claim 4, characterized in that: the application of the metal organic framework material with magnetic separation, double-wavelength self-correction and cyclic utilization in selective identification of the pesticide nitenpyram is provided.
6. The use of the metal-organic framework material for nitenpyram recognition detection according to claim 5, characterized in that: the metal organic framework material for nitenpyram identification and detection is used for high-selectivity and high-sensitivity identification of nitenpyram in a water body, and can be circularly used for nitenpyram concentration detection through simple magnetic separation.
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| CN107876014A (en) * | 2016-09-29 | 2018-04-06 | 天津工业大学 | A kind of synthetic method of hollow nucleocapsid magnetic metal organic framework composite material |
| CN109663135A (en) * | 2018-11-21 | 2019-04-23 | 上海师范大学 | ZIF-8 coats ferriferrous oxide nano-particle material and its preparation method and application |
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| CN107596391A (en) * | 2017-11-09 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of metal organic frame base nanometer diagnosis and treatment probe and products thereof and application |
| CN109663135A (en) * | 2018-11-21 | 2019-04-23 | 上海师范大学 | ZIF-8 coats ferriferrous oxide nano-particle material and its preparation method and application |
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