Copper metal complex and preparation method and application thereof
By preparing the copper metal complex [Cu2(NPTH)2(4,4′-BMIBP)2(H2O)4·6H2O]n, the problem of insufficient research on antibiotic detection and degradation in the existing technology was solved, and efficient and sensitive detection of nitrofurantoin and degradation of methylene dyes were achieved, which is suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANCHENG TEACHERS UNIV
- Filing Date
- 2023-04-25
- Publication Date
- 2026-07-24
AI Technical Summary
There is limited research on the fluorescent response of antibiotics to catalytic degradation of organic pollutants in existing technologies, and there is a lack of novel, stable and high-performance metal-organic framework materials.
A copper metal complex [Cu2(NPTH)2(4,4′-BMIBP)2(H2O)4·6H2O]n was prepared by mixing 4,4′-bis(2-methylimidazolyl)biphenyl, 3-nitrophthalic acid, and copper nitrate trihydrate, water, and N,N-dimethylacetamide solution, and reacting hydrothermally for 72 hours to obtain blue transparent blocky crystals.
It achieves highly sensitive detection of nitrofurantoin and photocatalytic degradation of methylene dyes, with high yield, easy separation, and good reproducibility, making it suitable for industrial production. It has rapid, qualitative, and sensitive detection and degradation capabilities.
Smart Images
Figure CN116478186B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organometallic coordination compound technology, specifically relating to a copper metal complex, its preparation method, and its application. Background Technology
[0002] In recent years, residual antibiotics in the environment have had a serious impact on human health and ecosystems. Therefore, rapid and accurate detection of antibiotics is urgently needed. Metal-organic framework (MOF) fluorescent sensing materials are considered one of the most promising detection methods and are widely used to identify harmful substances such as anions, cations, and small organic molecules. This method can simply detect the presence of analytes by observing changes in fluorescence intensity with analyte concentration. Compared to traditional analytical techniques, MOF-based fluorescent sensing offers advantages such as high precision, high sensitivity, small size, short response time, and good adaptability.
[0003] Publication number CN110128674 discloses a water-stable rare earth metal-organic framework material for fluorescent detection of sulfonamide antibiotics and its preparation method. However, there are still few studies on the fluorescent response of antibiotics and their simultaneous catalytic degradation of organic pollutants.
[0004] Therefore, it is particularly important to regulate the synthesis of a novel, stable MOF material with excellent performance and to develop its application in the fields of fluorescent sensing antibiotics and photocatalytic degradation of organic pollutants. Summary of the Invention
[0005] In view of this, the purpose of this invention is to address the problems existing in the prior art by providing a copper metal complex for detecting furazolidone and photocatalytic degradation of methylene dyes.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] A copper metal complex, the chemical formula of which is [Cu2(NPTH)2(4,4′-BMIBP)2(H2O)4·6H2O] n In this context, H2NPTH = 3-nitrophthalic acid, and 4,4′-BMIBP = 4,4′-bis(2-methylimidazolyl)biphenyl.
[0008] Furthermore, the structural formula of 4,4′-BMIBP,H2NPTH is as follows:
[0009]
[0010] A second objective of this invention is to provide a method for preparing the copper metal complex.
[0011] To achieve the above objectives, the present invention provides the following technical solution:
[0012] The method for preparing the copper metal complex includes the following steps:
[0013] (1) Mix 4,4'-bis(2-methylimidazolyl)biphenyl, 3-nitrophthalic acid and copper nitrate trihydrate in a molar ratio of 1:1:1, then add H2O and DMA and mix to obtain a mixture;
[0014] (2) The mixture from step (1) was reacted at 100°C for 72 hours. After the reaction was completed, the product was taken out and obtained by solid-liquid separation and washing. The resulting blue transparent block crystals were the copper metal complex.
[0015] Furthermore, in step (1), the molar volume ratio of 4,4'-bis(2-methylimidazolyl)biphenyl to 3-nitrophthalic acid, copper nitrate trihydrate, water, and DMA solution is 0.015 mmol:0.015 mmol:0.015 mmol:2.0 mL:0.5 mL.
[0016] A third objective of this invention is to provide the application of the aforementioned copper metal complex in the detection of furazolidone.
[0017] Furthermore, the present invention also claims protection for the application of the copper metal complex in the photocatalytic degradation of methylene dyes.
[0018] Compared with existing technologies, the preparation method disclosed in this invention is simple, has high yield, is easy to separate, has good reproducibility, high sensitivity, good catalytic efficiency, and high recovery rate. It can obtain a single crystal form, high-purity crystalline material, and is easy to industrialize. The product has fluorescent recognition capabilities for furantoin, which can be used for the detection of furantoin in aqueous solutions, and can also photocatalytically degrade methylene fuels. Compared with traditional detection and degradation methods, this method has advantages such as qualitative analysis, speed, sensitivity, high efficiency, and ease of operation. Attached Figure Description
[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0020] Figure 1 This is a diagram of the smallest asymmetric unit cell of the copper complex of the present invention.
[0021] Figure 2 This is a two-dimensional structural diagram of a copper complex.
[0022] Figure 3The image shows the powder XRD pattern of the copper complex.
[0023] Figure 4 This is a thermogravimetric diagram of a copper complex.
[0024] Figure 5 This is a fluorescence intensity diagram of the copper complex of the present invention against different concentrations of nitrofurantoin antibiotic (NFT) solutions.
[0025] Figure 6 This is a linear fit spectrum of the fluorescence peak ratio of the copper complex of the present invention and the concentration of nitrofurantoin (NFT) antibiotic.
[0026] Figure 7 This is a diagram showing the photocatalytic degradation of methylene blue (MB) by the copper complex of this invention.
[0027] Figure 8 This is a graph showing the photocatalytic decomposition rate of methylene blue (MB) by the copper complex of this invention. Detailed Implementation
[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0029] Example 1
[0030] A method for preparing a copper metal complex specifically includes the following steps:
[0031] (1) 4,4'-bis(2-methylimidazolyl)biphenyl: 3-nitrophthalic acid ligand: copper nitrate trihydrate = 1:1:1, add H2O (2.0 mL) and DMA (0.5 mL), mix and place in the polytetrafluoroethylene liner of a 25 mL hydrothermal reactor, mix and sonicate for 5 minutes to obtain a mixture;
[0032] (2) The above mixture was dried at 100°C for 72 hours, and the solid was separated after the product was removed;
[0033] (3) Wash the above solid three times with water to obtain blue transparent block crystals.
[0034] To further demonstrate the beneficial effects of the present invention and to better understand the present invention, the following test results further illustrate the properties and application performance of the series of mixed ligand organometallic coordination compounds described in the present invention. However, these tests should not be construed as limiting the present invention. The product properties obtained by other test results performed by those skilled in the art based on the above-described invention and the applications based on the above properties are also considered to fall within the protection scope of the present invention.
[0035] Experimental Example 1: Crystal Structure Determination
[0036] Select a single crystal of appropriate size using a microscope, and then use a Siemens (Bruker) SMART CCD diffractometer (graphite monochromator, Mo–Ka) at room temperature. Diffraction data were collected. Absorption correction was performed on the diffraction data using the SADABS program. Data reconstruction and structure analysis were performed using the SAINT and SHELLXTL programs, respectively. The coordinates of all non-hydrogen atoms were determined using the least squares method, and the positions of hydrogen atoms were obtained using the theoretical hydrogenation method. The crystal structure was then refined using the least squares method.
[0037] The copper complex of this invention belongs to the triclinic crystal system, with space group P-1 and cell parameters of [missing information]. α=96.2230(10)°, β=99.049(3)°, γ=97.564(2)°; In this compound, each copper atom coordinates with the nitrogen atoms of two 4,4'-bis(2-methylimidazolyl)biphenyl ligands, the two oxygen atoms of one 3-nitrophthalic acid ligand, and an oxygen atom from a coordinated water molecule to form the spatial configuration of CuO3N2, such as Figure 1 As shown, copper ions, 3-nitrophthalic acid, and 4,4'-bis(2-methylimidazolyl)biphenyl are interconnected to form a one-dimensional structure, as shown. Figure 2 As shown.
[0038] Experiment 2: Powder XRD
[0039] The powder X-ray diffraction of the copper complex of the present invention perfectly matches the diffraction peaks simulated by an ideal single crystal, indicating that the prepared copper complex crystal has high phase purity. Figure 3 As shown.
[0040] Experiment 3: Thermogravimetric Analysis of Copper Alloy
[0041] To investigate the thermal stability of the crystal, thermogravimetric analysis (TGA) was performed on the synthesized copper complex, yielding... Figure 4 The TG graph shown is composed of... Figure 4 It can be seen that the weight loss of this copper complex is mainly divided into two stages: the first stage is from room temperature to about 125°C, where the loss is mainly of free solvent on the crystal surface and in the pores; the second stage occurs between 165°C and 800°C, where the organic ligands are mainly decomposed and carbonized.
[0042] Experimental Example 4: Detection of Nitrofurantoin (NFT)
[0043] By measuring the fluorescence spectra of the synthesized copper complex in different concentrations of NFT antibiotics, the following results were obtained. Figure 5The fluorescence emission spectrum shown indicates that the fluorescence intensity gradually decreases with increasing NFT antibiotic concentration, exhibiting a significant fluorescence quenching effect.
[0044] Using the Stern-Volmer equation (I0 / I=1+K) SV [M]) calculated the relationship between (I0 / I-1) and NFT antibiotics, and plotted the results. Figure 6 The SV plot shown is a linear fit curve of the relative change ratio of fluorescence intensity to NFT antibiotic concentration. It can be seen that the two are linearly related in the low concentration range. Using the detection limit (LOD) formula, the detection limit of the synthesized copper complex for NFT antibiotic can be calculated to be 1.89 × 10⁻⁶. -4 M.
[0045] Experimental Example 5: Degradation of Methylene Dyes
[0046] Weigh 30 mg of the copper complex synthesized in this invention and add it to 50 mL of methylene blue aqueous solution (10 mg / L). Then add 5 μL of H2O2 and stir in the dark for 30 min to allow the complex surface to reach adsorption-desorption equilibrium. Then, while stirring, irradiate with a visible light lamp. Take 1 mL of the methylene blue aqueous solution every 10 min and measure the ultraviolet absorption spectrum of the solution (e.g., ...). Figure 7 As shown in the figure, the concentration of methylene blue was detected by absorbance, and the concentration ratio C / C0 versus time t (C0 is the initial concentration, and C is the concentration at time t) was used to measure the degradation efficiency (e.g., ...). Figure 8 (As shown). Photodegradation results showed that the complex achieved a degradation rate of up to 83.1% for methylene blue within 90 minutes, while the degradation rate without the complex was only 5.58%. (As shown) Figure 8 ).
[0047] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A copper metal complex for the detection and photocatalytic degradation of methylene dyes by nitrofurantoin, characterized in that, The chemical formula of the copper metal complex is [Cu2(NPTH)2(4,4'-BMIBP)2(H2O)4·6H2O] n In this context, H2NPTH = 3-nitrophthalic acid, and 4,4'-BMIBP = 4,4'-bis(2-methylimidazolyl)biphenyl.
2. A method for preparing a copper metal complex for the detection and photocatalytic degradation of methylene dyes as described in claim 1, characterized in that the step... include: (1) Mix 4,4'-bis(2-methylimidazolyl)biphenyl, 3-nitrophthalic acid and copper nitrate trihydrate in a molar ratio of 1:1:1, then add H2O and DMA and mix to obtain a mixture; (2) The mixture from step (1) was reacted at 100°C for 72 hours. After the reaction was completed, the product was taken out and obtained by solid-liquid separation and washing. The resulting blue transparent block crystals were the copper metal complex.
3. The method for preparing copper metal complexes for the detection and photocatalytic degradation of methylene dyes according to claim 2, characterized in that, The molar volume ratio of 4,4'-bis(2-methylimidazolyl)biphenyl to 3-nitrophthalic acid, copper nitrate trihydrate, water, and DMA solution in step (1) is 0.015 mmol:0.015 mmol:0.015 mmol:2.0 mL:0.5 mL.