CN113698616B - Preparation method and application of metal zinc coordination polymer - Google Patents

Preparation method and application of metal zinc coordination polymer Download PDF

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CN113698616B
CN113698616B CN202110927139.0A CN202110927139A CN113698616B CN 113698616 B CN113698616 B CN 113698616B CN 202110927139 A CN202110927139 A CN 202110927139A CN 113698616 B CN113698616 B CN 113698616B
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王炎
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Abstract

The invention provides a preparation method and application of a metal zinc coordination polymer, wherein the chemical formula of the metal zinc coordination polymer is as follows: [ Zn ] 2 (μ 2 ‑bcpb)(μ 4 ‑bcpb)(2,2'‑bipy) 2 ] n Wherein bcpb 2‑ For deprotonated 1, 4-bis (2' -carboxyphenoxy) benzene, 2,2' -bipy is 2,2' -bipyridine. The metal zinc coordination polymer is prepared by a hydrothermal method, namely: zn (NO) is added according to the mol ratio of 2:2:1 3 ) 2 ·6H 2 O, 2 '-bipyridine and 1, 4-bis (2' -carboxyphenoxy) benzene were added to a polytetrafluoroethylene tube, 1mL of N, N-dimethylformamide and 6mL of water were added, the pH was adjusted to 5.0 with 0.25mol/L NaOH, and the polytetrafluoroethylene tube was placed in a reaction vessel and reacted at 413K for 3 days. Cooling to room temperature, collecting colorless transparent block crystal, washing with distilled water, and vacuum drying. The metal zinc coordination polymer is a two-dimensional structure with binuclear zinc secondary structural units. The complex has good selectivity for detecting acetone and divalent copper ions in aqueous solution, can be used repeatedly at least five times, and can be used as a fluorescent probe for efficiently detecting acetone and divalent copper ions.

Description

Preparation method and application of metal zinc coordination polymer
Technical Field
The invention relates to the field of zinc coordination polymers, in particular to a preparation method and application of a metal zinc coordination polymer.
Background
Acetone is a liquid with aromatic odor, is flammable and volatile, is easily soluble in water and methanol, and has active chemical properties. Is harmful to human body, and is easy to cause poisoning by long-term contact with acetone, which is often manifested as shortness of breath, nausea, vomiting and headache. Copper is a metal with a purple-red luster and a density of 8.92g/cm 3 . Copper exists mainly in three forms of metallic copper, monovalent copper and divalent copper in nature, and is used as a trace element necessary for a human body, and trace copper ions are beneficial to the human body. However, excessive copper ions in the human body cause cirrhosis, diarrhea, vomiting, dyskinesia, and sensory neuropathy. Therefore, the detection of acetone and divalent copper ions in drinking water and industrial wastewater is of great importance, and the fluorescent probe with the advantages of simple synthesis, high identification speed, low cost and the like becomes a hotter detection method researched at present. Therefore, the design and synthesis of fluorescent probes for acetone and divalent copper ions have very important significance.
Disclosure of Invention
The invention aims to provide a preparation method of a coordination polymer with a two-dimensional structure constructed on the basis of transition metal zinc (II), 1, 4-bis (2 '-carboxyphenoxy) benzene and 2,2' -bipyridyl, and application of the coordination polymer as a fluorescent probe for detecting acetone and divalent copper ions in an aqueous solution.
In order to realize the purpose, the invention is realized by the following technical scheme:
a metal zinc coordination polymer having the chemical formula: [ Zn ] 2 (μ 2 -bcpb)(μ 4 -bcpb)(2,2'-bipy) 2 ] n Wherein bcpb 2- Is deprotonated 1, 4-bis (2' -carboxyphenoxy) benzene, 2,2' -bipy is 2,2' -bipyridine, n is the degree of polymerization, and the structural formula is as follows:
Figure BDA0003209659100000021
the metal zinc complex belongs to a triclinic system, and the space group is P1. The asymmetric unit is composed of one Zn atom, one 2,2' -bipyridine and two 1/2 main ligands. Zn atom is penta-coordinated and forms triangular biconical ZnO 3 N 2 The unit, Zn atom coordinates with three oxygen atoms from different ligand carboxylic acids and two N atoms from 2,2' -bipyridine, respectively, forming a distorted trigonal bipyramidal geometric configuration. The bond length of Zn-O bond is in the range of
Figure BDA0003209659100000022
Between, the bond lengths of the Zn-N bonds are 2.1393(18) and
Figure BDA0003209659100000023
the included angle of O-Zn-O is 76.05(6) -133.10(6) °. X-ray confirmed powder diffraction confirmed that the crystalline sample was homogeneous and stable.
The invention provides a preparation method of the metal zinc coordination polymer, which comprises the following steps:
step 1: zn (NO) is added according to the molar ratio of 2:2:1 3 ) 2 ·6H 2 O, 2' -bipyridine and 1,4Adding bis (2' -carboxyphenoxy) benzene into a polytetrafluoroethylene tube, adding 1mL of N, N-dimethylformamide and 6mL of water, and adjusting the pH value to 5.0 by using a NaOH solution;
step 2: and (3) placing the polytetrafluoroethylene tube in a stainless steel reaction kettle, sealing, reacting for 3 days at 413K, cooling to room temperature to precipitate colorless transparent blocky crystals, washing with distilled water, and drying in vacuum to obtain the metal zinc coordination polymer.
Further, the concentration of the NaOH solution in the step 1 is 0.25 mol/L.
The invention also provides application of the metal zinc coordination polymer as a fluorescent probe to detection of acetone and divalent copper ions in water.
Compared with the prior art, the invention has the following beneficial effects:
the zinc coordination polymer is synthesized under the hydrothermal condition, the preparation process is simple, and the yield and the purity are high. Thermogravimetric analysis shows that the structure decomposes above 243 ℃ and the practical temperature range is below 243 ℃. The zinc coordination polymer is constructed based on 1, 4-bis (2 '-carboxyphenoxy) benzene, wherein 1, 4-bis (2' -carboxyphenoxy) benzene is a semi-rigid ligand, a benzene ring can freely rotate around an ether linkage oxygen atom, and the oxygen atom at the center of the ligand can provide electrons for the benzene ring. Wherein, mu 4 -COO - The carboxyl group connects two zinc ions to form [ Zn ] 2 (μ 4 -COO)(2,2'-bipy) 2 ] 2+ A dual core secondary building block. The complex has unique fluorescence selectivity on acetone and divalent copper ions in aqueous solution as a fluorescent probe, can effectively and selectively detect the acetone and the divalent copper ions, has the detection limit of 0.0150 percent M on the acetone and has the detection limit of Cu 2+ Has a detection limit of 7.2X 10 -7 M, and the complex can be used repeatedly at least five times. The complex is in aqueous solution to acetone and Cu 2+ Has higher sensitivity and lower detection limit, thereby having greater application prospect in the field of fluorescent probe detection.
Drawings
FIG. 1 is a crystal structure diagram of a zinc complex of the present invention.
FIG. 2 is an X-ray powder diffraction pattern of a zinc complex of the present invention.
FIG. 3 is a thermogravimetric analysis of the zinc complex of the present invention.
FIG. 4 is a fluorescence spectrum of the zinc complex of the present invention mixed with various organic small molecule solutions in an aqueous solution.
FIG. 5 is a fluorescence spectrum of a zinc complex of the present invention added with acetone of different contents in an aqueous solution.
FIG. 6 is a linear calibration curve of fluorescence of the zinc complex of the present invention with different amounts of acetone added to the aqueous solution.
FIG. 7 is a fluorescence spectrum of a zinc complex of the present invention mixed with various metal cation solutions in an aqueous solution.
FIG. 8 shows that Cu with different concentrations is added into an aqueous solution by the zinc complex of the invention 2+ Fluorescence spectrum of (2).
FIG. 9 shows that the zinc complex of the present invention is added with Cu of different concentrations in an aqueous solution 2+ Linear calibration curve of fluorescence.
FIG. 10 shows the detection of Cu by the zinc complex of the present invention 2+ Five cycles of the experiment fluorescence spectrogram.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
Preparation of Zinc coordination polymers
H is to be 2 bcpb(17.5mg,0.05mmol)、Zn(NO 3 ) 2 ·6H 2 O (29.7mg,0.1mmol), 2' -bipy (15.6mg,0.1mmol) were added to a 25mL polytetrafluoroethylene tube, and DMF (1.0mL) and H were added 2 O (6.0mL), adjusted to pH 5.0 with 0.5mL of 0.25mol/L NaOH solution, transferred to the reaction kettle and reacted in an oven at 413K for 72 hours, then filtered, dried and cooled to room temperature to give colorless and transparent crystals in the form of a lump with a yield of 55.9%.
And (3) determining the crystal structure of the zinc complex:
the crystal structure is measured by X-ray diffraction, Mo-K alpha rays are monochromatized by a Bruker D8Venture detector through a graphite monochromator in a scanning mode of omega, and the temperature of collected data is 293K. The raw data was restored by SAINT and then absorption corrected using SADABS. The crystal structure is obtained by directly solving SHELXL-97. The detailed crystal determination data are shown in table 1. The crystal structure is shown in a one-dimensional structure diagram in figure 1.
TABLE 1 crystallographic data for Zinc complexes
Figure BDA0003209659100000041
Figure BDA0003209659100000051
Powder diffraction:
the X-ray powder diffraction is shown in fig. 2, and the experimental diffraction pattern is consistent with the powder diffraction pattern simulated according to the crystal structure, which indicates that the phase of the crystal sample is uniform.
Thermogravimetric analysis of zinc coordination polymer:
the results of thermogravimetric analysis show that the main structure of the zinc coordination polymer is decomposed at the temperature of 243 ℃ or higher, which shows that the zinc coordination polymer of the invention is suitable for the temperature below 243 ℃, and the results are shown in figure 3.
Example 2 Selective recognition of acetone in Water by Metal Zinc Complex as fluorescent Probe
Firstly, taking different organic small molecule solutions (methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, ethylene glycol, acetonitrile, acetone and dimethyl sulfoxide), dissolving 5mg of the metal zinc complex in 50mL of water, performing ultrasonic treatment for 30min, and precipitating for three days. And (3) taking supernatant liquid, respectively adding different organic small molecule solutions, and measuring the fluorescence emission intensity of the supernatant liquid under the excitation of 250nm, wherein the complex has unique fluorescence selectivity on acetone as shown in figure 4.
Example 3 sensitivity of Metal Zinc Complex as fluorescent Probe for identifying acetone in Water
5mg of the metal zinc complex was dissolved in 50mL of water, sonicated for 30min, and allowed to settle for three days, to form a suspension containing the metal zinc complex. The supernatant was taken and the suspension of the complex showed very strong fluorescence at 324nm, measured under excitation at a wavelength of 250 nm. As can be seen from the titration curve of FIG. 5, the fluorescence intensity of the solution gradually decreased as the acetone concentration in the system increased. Furthermore, as shown in fig. 6, at low concentrations, the quenching effect can be fitted as a function of: i is 0 /I＝1.9525V Acetone/H2O +0.9446，I 0 Calculating the correlation coefficient R for the initial luminous intensity and I for the luminous intensity after adding acetone 2 Has a value of 0.9812. LOD 3S based on equation B /S(S B S is the slope of the linear relationship of acetone content to fluorescence intensity plotted against the standard deviation of five blank measurements relative to aqueous solution) was calculated to have a detection limit of 0.0150% M for acetone.
Example 4 Metal Zinc Complex as fluorescent Probe for Cu in Water 2+ Selective identification of
First, 5mL of the solution was prepared at a concentration of 1X 10 -3 mol/L of different cation solutions (Na) + 、Fe 3+ 、Cr 3+ 、Cd 2+ 、Cu 2+ 、K + 、Mg 2+ 、Ni 2+ 、Co 2+ 、Ba 2+ 、Zn 2+ 、Mn 2+ 、Ca 2+ ) Then, 5mg of the metal zinc complex was dissolved in 50mL of water, sonicated for 30min, and precipitated for three days. Collecting supernatant, adding metal cation solution, measuring fluorescence emission intensity under 250nm excitation, and adding Cu as shown in FIG. 7 2+ Can quench the fluorescence of the complex.
Example 5 identification of Cu in Water by Metal Zinc Complex as fluorescent Probe 2+ Sensitivity of (2)
5mg of this metal zinc complex was dissolved in 50mL of water, sonicated for 30min, and allowed to settle for three days, allowing it to form a complex-containing suspension. The supernatant was taken and the suspension of the complex showed very strong fluorescence at 324nm, measured under excitation at a wavelength of 250 nm.As can be seen from the titration curves of FIG. 8, with Cu in the system 2+ The fluorescence intensity of the solution gradually decreases with increasing concentration. Furthermore, as shown in FIG. 9, at low concentrations, the quenching effect can be handled by the Stern-Volmer equation: i is 0 /I＝1+K SV ×[M]，I 0 Is the initial fluorescence intensity of the complex, I is the addition of Cu 2+ Fluorescence intensity of the post-complex, [ M]Is Cu 2+ Concentration of (A), K SV Is the quenching constant. K SV Calculated value of (A) is 5.7X 10 4 M -1 . Obtained by calculating the detection limit, the complex is used for Cu 2+ Has a detection limit of 7.2X 10 -7 And M. Illustrating the fluorescent probe to Cu in an aqueous solution 2+ Has higher sensitivity and lower detection limit, thereby having larger application prospect.
Example 6 identification of Cu in Water by Metal Zinc Complex as fluorescent Probe 2+ Recycling property of (2)
5mg of the fluorescent probe was immersed in 10mL of an aqueous solution, and after three days, the supernatant and the supernatant were measured separately and Cu was added 2+ Centrifuging, washing, drying, adding 10mL water, ultrasonic treating for 30min, precipitating for three days, measuring supernatant, adding Cu into supernatant, and collecting supernatant 2+ The cycle is five times. FIG. 10 is a fluorescence spectrum of the fluorescent probe after five cycles, illustrating the recyclability of the probe.

Claims (4)

1. A metal zinc coordination polymer is characterized in that the chemical formula is as follows: [ Zn ] 2 (μ 2 -bcpb)(μ 4 -bcpb)(2,2'-bipy) 2 ] n Wherein bcpb 2- Is deprotonated 1, 4-bis (2' -carboxyphenoxy) benzene, 2,2' -bipy is 2,2' -bipyridine, n is the degree of polymerization, and the structural formula is as follows:
Figure FDA0003209659090000011
2. the method for preparing a zinc metal coordination polymer according to claim 1, comprising the steps of:
step 1: zn (NO) is added according to the molar ratio of 2:2:1 3 ) 2 ·6H 2 Adding O, 2 '-bipyridyl and 1, 4-bis (2' -carboxyphenoxy) benzene into a polytetrafluoroethylene tube, adding 1mL of N, N-dimethylformamide and 6mL of water, and adjusting the pH value to 5.0 by using a NaOH solution;
step 2: and (3) placing the polytetrafluoroethylene tube in a stainless steel reaction kettle, sealing, reacting for 3 days at 413K, cooling to room temperature to separate out colorless transparent blocky crystals, washing with distilled water, and drying in vacuum to obtain the metal zinc coordination polymer.
3. The method of claim 2, wherein the concentration of the NaOH solution in step 1 is 0.25 mol/L.
4. The use of a metal zinc coordination polymer according to claim 1, wherein said metal zinc coordination polymer is used as a fluorescent probe for the detection of acetone and cupric ions in water.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006248989A (en) * 2005-03-10 2006-09-21 Kyoto Univ Porous coordination polymer and catalyst comprising the same
CN111303443A (en) * 2020-03-03 2020-06-19 山西大学 Zinc coordination polymer and preparation method and application thereof
CN112175196A (en) * 2020-10-16 2021-01-05 山西大学 Preparation method and application of two-dimensional binuclear manganese coordination polymer
CN113150292A (en) * 2021-02-09 2021-07-23 山西大学 Preparation method and application of one-dimensional trinuclear zinc coordination polymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006248989A (en) * 2005-03-10 2006-09-21 Kyoto Univ Porous coordination polymer and catalyst comprising the same
CN111303443A (en) * 2020-03-03 2020-06-19 山西大学 Zinc coordination polymer and preparation method and application thereof
CN112175196A (en) * 2020-10-16 2021-01-05 山西大学 Preparation method and application of two-dimensional binuclear manganese coordination polymer
CN113150292A (en) * 2021-02-09 2021-07-23 山西大学 Preparation method and application of one-dimensional trinuclear zinc coordination polymer

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