Cu(i) complex, method of preparation and use

Abstract

The application belongs to the technical field of compound synthesis, and discloses a Cu(I) complex, a preparation method and application. The preparation method adopts a replacement method, and performs a complex reaction on triphenylphosphine PPh3 and 1,10-phenanthroline-5,6-dione pheno ligand and a copper salt to prepare the Cu(I) complex. The Cu(I) complex synthesized by the application is smooth on the surface and needle-shaped in shape. The best adsorption conditions are that the best dosage is 40 mg, the best time is 80 min, and the best temperature is 60 DEG C; the best ultraviolet light catalysis conditions are that the best dosage is 30 mg, the best light irradiation time is 100 min, and the best temperature is 70 DEG C. The degradation rate can reach 96.1% under the best conditions of the application. The detection limits of nickel and copper heavy metal ions are 5*10 ‑7 mol / L and 5*10 ‑8 mol / L respectively.

Description

Technical Field

[0001] This invention belongs to the field of compound synthesis technology, and particularly relates to a Cu(I) complex, its preparation method and application. Background Technology

[0002] Cu(I) complexes are widely used in many fields such as catalysts, energy, medicine, environment and information due to their low price, diverse spatial structures and unique photochemical and photophysical properties.

[0003] Common synthetic methods for triphenylphosphine copper (I) complexes include substitution, redox, electrochemical and direct addition methods.

[0004] Substitution method: Some weaker coordinating groups in the complex, such as NO3 - The most common method for synthesizing mixed complexes is to replace MeCN and other groups with other groups to form new complexes.

[0005] Redox method: This method utilizes the reducing and coordinating properties of organophosphorus ligands to directly react copper(II) compounds with PPh3 to generate copper(I) complexes containing triphenylphosphine, or to obtain copper(I) complexes containing triphenylphosphine using metallic copper powder as a starting material. These products are often used as substrates to synthesize complexes with special structures and properties, including mixed ligands.

[0006] Electrochemical method: This method utilizes the complex formed by the electrochemical reaction between a metal and ligands at an electrode. Typically, Pt is the cathode and Cu is the anode. An external electric field is then applied to oxidize Cu to Cu. + Cu + Forming complexes with ligands is a method that often takes place in one step, resulting in complexes with high purity.

[0007] Direct addition method: This method involves the direct addition reaction between a monovalent copper salt or complex and a ligand (including small molecule insertion) to form a complex.

[0008] With the continuous development of various industries and the gradual increase in the world's population, the consumption of water for production and daily life is increasing, as is the amount of wastewater discharged. Wastewater treatment has become an important research topic for various countries. Currently, the main sources of water pollution are urban domestic sewage and industrial wastewater, and the effective treatment of these organic wastewaters has become a research hotspot. Traditional treatment methods, such as biodegradation, adsorption, coagulation-sedimentation, chemical oxidation, and membrane separation, have problems such as low removal efficiency, secondary pollution, and high investment costs. Currently, photocatalytic degradation of organic pollutants is receiving more research, as it has better degradation effects and does not produce secondary pollution.

[0009] With the advancement of industrial development and the continuous expansion of human activities, numerous forms of pollution have emerged. Environmental pollution generally includes several major categories such as air pollution, water pollution, solid waste pollution, noise pollution, radioactive pollution, and heavy metal pollution. Among these, heavy metal pollution exists in the air, in everyday products, and even in food, posing a significant threat to the natural environment and human health. Therefore, the detection and control of heavy metal ions has always been a major focus of environmental science research.

[0010] The selection of heavy metal ion detection methods mainly considers factors such as selectivity, sensitivity, accuracy, linear range, and analysis speed. Common methods for heavy metal detection include atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), atomic emission spectrometry (AES), ultraviolet spectrophotometry (UVS), electrochemical methods, and inductively coupled plasma mass spectrometry (ICP-MS). Many chemists and environmental scientists have researched heavy metal ion recognition agents, striving to develop new ones. Among these, fluorescent heavy metal ion recognition agents, utilizing the unique optical properties of fluorescent molecules, offer a convenient method with higher sensitivity and faster analysis speed for heavy metal ion identification and detection, and are therefore widely welcomed by researchers.

[0011] Atomic absorption spectrometry (AAS) is a method for quantitative elemental analysis based on the resonance absorption of characteristic atomic lines of the same element by the ground-state atomic vapor. Widely used methods include flame atomic absorption spectrometry and graphite furnace atomic absorption spectrometry (non-flame atomic absorption spectrometry). While flame atomic absorption spectrometry is simple to operate, its low atomization efficiency makes it difficult to improve its sensitivity. Graphite furnace atomic absorption spectrometry (GF-AAS), on the other hand, requires less sample and achieves near 100% atomization efficiency. However, it has lower instrument precision and is more complex to operate.

[0012] Atomic fluorescence spectrometry (AFS) is an analytical method that uses the absorption of radiation of a specific wavelength by ground-state atoms (generally in a vapor state) to excite them to a higher energy state, and then they transition back to the ground state, emitting fluorescence of a characteristic wavelength in the form of light radiation. The advantages of this method are high sensitivity, low detection limits (e.g., the detection limit for silver ions is 0.01 ng / mL, and the detection limit for cadmium ions is 0.001 ng / mL), a wide linear range, inexpensive instrumentation, and the ability to perform simultaneous determination of multiple elements.

[0013] Atomic emission spectrometry (AES) is a method for quantitative and qualitative analysis of elements in a substance based on the characteristic spectra emitted by gaseous atoms or ions of the analyte after excitation. Advantages of AES include high sensitivity, wide linear range, good selectivity, and high analytical efficiency; it can analyze more than 70 elements. However, it cannot detect non-metallic elements or has low sensitivity, and the spectrometers are relatively expensive.

[0014] The basic principle of electrochemical analysis (EC) is to analyze the relationship between the electrochemical properties of the analyte in solution (such as conductivity, potential, current, and charge) and its concentration. Depending on the electrical parameters measured, it can be divided into potentiometric analysis, conductivity analysis, coulometric analysis, and polarographic analysis. Among these, polarography and cyclic voltammetry are used for metal ion measurement. Electrochemical analysis methods have advantages such as high sensitivity, fast analysis speed, easy automation, and good reproducibility. However, electrochemical analysis methods are susceptible to interference, have limited electrode lifespan, and are sensitive to changes in temperature and flow rate.

[0015] Inductively coupled plasma mass spectrometry (ICP-MS) is a mass spectrometry method that uses high-frequency inductively coupled plasma as an ion source. Compared with other methods, ICP-MS has a wide linear range, fewer interferences, requires smaller sample volumes, and offers faster analysis speed, allowing for the simultaneous determination of multiple elements. However, its main drawback is the high cost of the required equipment, which limits its widespread applicability.

[0016] In summary, industrial wastewater and urban sewage have caused serious damage to the ecological environment, and pollution problems in agriculture have become prominent. In particular, there is an increasing amount of pollutants such as organic pollutants and heavy metals, which are easy to accumulate, cause serious harm, and are not easily degraded by nature's self-purification process. This not only seriously restricts the sustainable development of society, but also poses a serious threat to the physical and mental health of the public.

[0017] Based on the above analysis, the problems and defects of the existing technology are as follows: the existing technology does not utilize the excellent photo-generating ability of phosphorescent copper material to photocatalytically degrade organic pollutants; at the same time, its fluorescence properties can also be used for the detection of heavy metal ions. This means that the existing technology cannot simultaneously perform the degradation rate of organic pollutants and the detection of heavy metal ions, resulting in high pollution treatment costs. Summary of the Invention

[0018] To overcome the problems existing in related technologies, the present invention discloses a Cu(I) complex, its preparation method, and its application.

[0019] The technical solution is as follows: A Cu(I) complex for the degradation of organic dye wastewater and the detection of heavy metal ions, with the molecular formula [Cu(PPh3)2(pheno)]BF4 and the structural formula as follows:

[0020]

[0021] Another objective of this invention is to provide a method for preparing Cu(I) complexes. This method employs a substitution method, reacting triphenylphosphine PPh3 and 1,10-o-phenanthroline-5,6-dione pheno ligand with copper salt [Cu(CH3CN)4]BF4 to prepare the Cu(I) complex. Specifically, the method includes:

[0022] S1: Add acetonitrile, copper tetrafluoroborate tetraacetonitrile [Cu(CH3CN)4]BF4 and triphenylphosphine PPh3 to a flask, then add 1,10-o-diazaphenanthroline-5,6-dione pheno, and stir the mixture thoroughly on a magnetic stirrer.

[0023] S2: Add diethyl ether until a precipitate forms, let stand, filter, and air dry to obtain the Cu(I) complex.

[0024] In step S1, the molar ratio of [Cu(CH3CN)4]BF4:triphenylphosphine:1,10-o-diazaphenanthroline-5,6-dione is 1:2:1.

[0025] In step S1, the reaction formulas for tetrafluoroborate tetraacetonitrile [Cu(CH3CN)4]BF4, triphenylphosphine PPh3, and 1,10-o-diazaphenanthroline-5,6-dione pheno are as follows:

[0026] [Cu(CH3CN)4]BF4+2PPh3+pheno→[Cu(PPh3)2(pheno)]BF4+4CH3CN.

[0027] Another objective of this invention is to provide an application of Cu(I) complexes in the degradation of organic dye wastewater. This application is achieved using Cu(I) complexes and takes methyl orange solution as the degradation target. A single-factor method is used to analyze the effects of the amount of Cu(I) complexes as catalysts, temperature, and time on the degradation effect of methyl orange under adsorption and ultraviolet light conditions.

[0028] Furthermore, under the adsorption conditions of constant temperature at 30℃ and standing for 30 min, the methyl orange solution was degraded, and the mass-volume ratio of Cu(I) complex to methyl orange solution was 4:1.

[0029] The methyl orange solution was degraded by constant temperature at 30℃. The mass-volume ratio of Cu(I) complex catalyst to methyl orange solution was 2:1, and the adsorption equilibrium time was 80 min.

[0030] The adsorption conditions were: Cu(I) complex catalyst to methyl orange solution at a mass-to-volume ratio of 2:1, standing for 30 min, and temperature of 60℃.

[0031] Furthermore, under constant temperature of 20℃ and UV irradiation for 30 min, the methyl orange solution was degraded, and the mass-volume ratio of Cu(I) complex to methyl orange solution was 3:1.

[0032] The methyl orange solution was degraded by standing at a constant temperature of 20℃. The mass-volume ratio of Cu(I) complex to methyl orange solution was 3:1. Under ultraviolet light irradiation, the highest photocatalytic degradation rate was achieved in 100 min.

[0033] The methyl orange solution was degraded by a Cu(I) complex to methyl orange solution mass-volume ratio of 1:1, allowed to stand for 30 min, and then subjected to ultraviolet light at a temperature of 70℃.

[0034] Another object of the present invention is to provide an application of Cu(I) complexes in the detection of heavy metal ions, wherein the application is implemented using the Cu(I) complexes, and the application includes:

[0035] Multiple concentration gradient Cu(I) complex solutions were prepared using N,N-dimethylformamide as a solvent. The concentrations corresponding to the absorption peaks of the Cu(I) complex were detected using a UV analyzer. Then, at these concentrations, mixed solutions of seven heavy metal ions were prepared. The Cu(I) complex solutions and the mixed solutions of heavy metal ions were detected using a fluorescence phosphorescent chemiluminescence spectrophotometer to obtain fluorescence emission peaks. Two heavy metal ions with distinct emission peaks were selected, and their detection limits were determined. The two heavy metal ions were then prepared into mixed solutions and Cu(I) complex solutions with concentration gradients, and the emission peaks were compared with those of the Cu(I) complex solutions to obtain the detection limits of the two heavy metal ions.

[0036] Furthermore, the two heavy metal ions with distinct emission peaks are selected as nickel ions and copper ions;

[0037] Fluorescence detection was performed on product solutions containing different concentrations of nickel and copper ions, and the detection limits for the two heavy metal ions were found to be 5*10⁻⁶. -7 mol / L and 5*10 -8 mol / L.

[0038] Another object of the present invention is to provide an application of Cu(I) complexes in the preparation of composite materials for wastewater treatment and environmental pollution treatment.

[0039] Combining all the above technical solutions, the beneficial effects of this invention are as follows: This invention mainly analyzes the adsorption and photocatalytic capabilities of Cu(I) complexes; at the same time, it analyzes their ability to detect heavy metal ions.

[0040] This experiment employed a substitution method, using [Cu(CH3CN)4]BF4, triphenylphosphine (PPh3), and 1,10-o-phenanthroline-5,6-dione (pheno) as raw materials and acetonitrile as solvent to prepare a Cu(I) complex. Methyl orange was used as a simulated organic pollutant, and the effects of different dosages, times, and temperatures on the degradation efficiency were investigated using a single-factor method. Simultaneously, experiments were conducted on its detection of heavy metal ions. Finally, the Cu(I) complex was characterized by XRD, IR, and SEM analysis to obtain the P, N, and Cu... + Coordination status, product composition, crystal form, particle size, and microstructure, etc.

[0041] Experimental results show that the synthesized Cu(I) complex has a smooth surface and a needle-like shape. Based on the experimental results, the optimal adsorption conditions for the catalyst are: optimal dosage of 40 mg, optimal time of 80 min, and optimal temperature of 60 °C; the optimal UV photocatalytic conditions are: optimal dosage of 30 mg, optimal irradiation time of 100 min, and optimal temperature of 70 °C. Under the optimal conditions of this invention, the degradation rate can reach 96.1%. Under the detection of a three-way UV spectrometer and a fluorescence phosphorescence chemiluminescence spectrophotometer, the detection limits for nickel and copper heavy metal ions are 5*10⁻⁶. -7 mol / L and 5*10 -8 mol / L. Attached Figure Description

[0042] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure;

[0043] Figure 1 This is a flowchart of the preparation method of Cu(I) complex provided in the embodiments of the present invention;

[0044] Figure 2 This is the infrared spectrum of the Cu(I) complex provided in the embodiments of the present invention;

[0045] Figure 3 This is an X-ray diffraction pattern of the Cu(I) complex provided in an embodiment of the present invention;

[0046] Figure 4 This is an image of the Cu(I) complex provided in the embodiments of the present invention, magnified 20,000 times and formed under a scanning electron microscope;

[0047] Figure 5 This is an image of the Cu(I) complex provided in this embodiment of the invention, magnified 10,000 times and formed under a scanning electron microscope;

[0048] Figure 6This is an image of the Cu(I) complex provided in an embodiment of the present invention, magnified 3000 times and formed under a scanning electron microscope;

[0049] Figure 7 This is an image of the Cu(I) complex provided in the embodiments of the present invention, magnified 1000 times and formed under a scanning electron microscope;

[0050] Figure 8 This is an image of the Cu(I) complex provided in an embodiment of the present invention, magnified 500 times and formed under a scanning electron microscope;

[0051] Figure 9 This is a graph showing the effect of catalyst dosage on methyl orange adsorption provided in the embodiments of the present invention;

[0052] Figure 10 This is a graph showing the effect of adsorption time on the adsorption of methyl orange, provided in an embodiment of the present invention.

[0053] Figure 11 This is a graph showing the effect of temperature on the adsorption of methyl orange, provided in an embodiment of the present invention.

[0054] Figure 12 This is a graph showing the effect of catalyst dosage on the degradation of methyl orange according to embodiments of the present invention;

[0055] Figure 13 This is a graph showing the effect of light exposure time on the degradation of methyl orange, provided in an embodiment of the present invention.

[0056] Figure 14 This is a graph showing the effect of temperature on the degradation of methyl orange, provided in an embodiment of the present invention.

[0057] Figure 15 This is the ultraviolet absorption peak diagram of the product provided in the embodiments of the present invention;

[0058] Figure 16 This is a fluorescence emission peak diagram of the product and heavy metal ions provided in the embodiments of the present invention;

[0059] Figure 17 This is a fluorescence emission peak diagram of nickel ions and products provided in the embodiments of the present invention;

[0060] Figure 18 This is a fluorescence emission peak diagram of copper ions and products provided in the embodiments of the present invention. Detailed Implementation

[0061] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0062] The innovative aspects of the Cu(I) complex, preparation method, and application provided in this invention are as follows:

[0063] This invention designs and synthesizes a mononuclear phosphorescent copper and analyzes its application in the degradation of organic dye wastewater and the detection of heavy metal ions. This provides a theoretical basis for the degradation of organic dye wastewater and the detection of heavy metal ions.

[0064] This invention employs a solution method to prepare a Cu(I) complex by coordinating triphenylphosphine (PPh3) and 1,10-o-phenanthroline-5,6-dione (pheno) ligand with a copper salt ([Cu(CH3CN)4]BF4). Acetonitrile was added to a 25 mL flask, followed by copper tetrafluoroborate-acetonitrile and triphenylphosphine, and then 1,10-o-phenanthroline-5,6-dione. The mixture was stirred thoroughly on a magnetic stirrer to obtain a blood-red solution. The solution was poured into a beaker, and diethyl ether was added until a yellow precipitate formed. After standing for 20 minutes, the mixture was filtered through a funnel and air-dried to obtain the final product. The product was characterized by XRD, IR, and SEM analysis to study the relationship between P, N, and Cu. + Coordination status, product composition, crystal form, particle size, and microstructure, etc.

[0065] Then, using methyl orange solution as the degradation target, the effects of catalyst dosage, temperature, and time on the degradation efficiency of methyl orange were analyzed using a single-factor method under adsorption and ultraviolet irradiation conditions. Simultaneously, solutions of seven heavy metal ions were prepared, and the fluorescence emission peaks of the product were used to detect these seven heavy metal ions, yielding the detection limits for nickel and copper ions.

[0066] This invention innovatively proposes a method for preparing [Cu(PPh3)2(pheno)]BF4, filling the gap in the photodegradation and heavy metal ion detection of [Cu(PPh3)2(pheno)]BF4, and effectively promoting the development of luminescent Cu(I) complexes.

[0067] In this invention, methyl orange is used to simulate organic pollutants. The optimal factors affecting degradation are obtained by screening the dosage, time, and temperature of Cu(I) complexes. At the same time, [Cu(PPh3)2(pheno)]BF4 is used to detect different metal ions, and the detection limit is determined.

[0068] The process described in this invention is simple to operate, has mild reaction conditions, low raw material prices, and low process costs, making it promising for industrial production.

[0069] Example 1: This embodiment of the invention provides a Cu(I) complex, which is used for the degradation of organic dye wastewater and the detection of heavy metal ions. The molecular formula is [Cu(PPh3)2(pheno)]BF4, and the structural formula is:

[0070]

[0071] Example 2, as Figure 1 As shown, this invention provides a method for preparing Cu(I) complexes. This method employs a substitution method, in which triphenylphosphine PPh3 and 1,10-o-diazaphenanthroline-5,6-dione pheno ligands are reacted with copper salt [Cu(CH3CN)4][BF4] to prepare Cu(I) complexes. Specifically, the method includes the following steps:

[0072] S1: First, add acetonitrile to the flask, then add copper tetrafluoroborate tetraacetonitrile [Cu(CH3CN)4][BF4] and triphenylphosphine PPh3; then add 1,10-o-diazaphenanthroline-5,6-dione pheno and stir the reaction thoroughly on a magnetic stirrer.

[0073] S2: Add diethyl ether until a precipitate forms, let stand, filter, and air dry to obtain the final product Cu(I) complex.

[0074] In the above embodiments, the descriptions of each embodiment have different focuses. For parts that are not described in detail or recorded in a certain embodiment, please refer to the relevant descriptions of other embodiments.

[0075] To further illustrate the effects of the embodiments of the present invention, the following experiments were conducted.

[0076] Preparation and analysis of Cu(I) complexes:

[0077] The experimental reagents and instruments used in the product manufacturing process are as follows: The experimental reagents used in this experiment are copper powder, copper oxide powder, tetrafluoroboric acid, triphenylphosphine and 1,10-o-diazaphenanthroline-5,6-dione, and acetonitrile is used as the solvent.

[0078] First, add acetonitrile to a 25 mL flask, then add copper tetrafluoroborate tetraacetonitrile and triphenylphosphine. Stir on a magnetic stirrer until the reaction is complete. Then add 1,10-o-diazaphenanthroline-5,6-dione, [Cu(CH3CN)4]BF4:triphenylphosphine:1,10-o-diazaphenanthroline-5,6-dione = 1:2:1; the reaction formula is:

[0079] [Cu(CH3CN)4]BF4+2PPh3+pheno→[Cu(PPh3)2(pheno)]BF4+4CH3CN;

[0080] Stir together for 30 minutes. Pour the completely reacted solution into a beaker, add ether until turbidity is formed, let stand for 20 minutes, filter through a funnel, and air dry to obtain the final product. The reagents and materials used in the experiment are shown in Table 1.

[0081] Table 1 Chemicals used in the experiment

[0082]

[0083]

[0084] Select experimental instruments and perform experimental procedures:

[0085] The preparation of Cu(I) complexes includes:

[0086] (1) Place the magnetic stirrer flat on the operating platform and turn on the power.

[0087] (2) Measure 2 mL of acetonitrile into a 25 mL round-bottom flask using a graduated cylinder. Weigh copper tetrafluoroborate tetraacetonitrile ([Cu(CH3CN)4]BF4) (1 mmol, 0.316 g) using an analytical balance and immediately add it to the 25 mL round-bottom flask. Then add the weighed triphenylphosphine (PPh3) (2 mmol, 0.5246 g). Place the 25 mL round-bottom flask on a magnetic stirrer, add a stir bar, turn on the stirring switch, and stir at medium speed.

[0088] (3) After the solution is completely dissolved, add the weighed 1,10-o-phenanthroline-5,6-dione (pheno) (1 mmol, 0.2102 g) to the flask and stir for 30 minutes.

[0089] (4) Stop stirring, pour the blood-red solution into a 50 ml test tube, open the fume hood, add 10 ml of anhydrous ether, the solution becomes turbid and a yellow precipitate forms, let stand for 20 minutes.

[0090] (5) Take a funnel, put it into a 50mL test tube, fix it on an iron frame, attach the folded filter paper to the funnel wall with water, filter the filtrate completely, and air dry to obtain the desired yellow solid product [Cu(PPh3)2(pheno)]BF4.

[0091] The structural formulas of [Cu(PPh3)2(pheno)]BF4, i.e., the Cu(I) complex and 1,10-o-diazaphenanthroline-5,6-dione, are as follows:

[0092]

[0093] The experimental principle is as follows:

[0094] [Cu(CH3CN)4]BF4+2PPh3+pheno→[Cu(PPh3)2(pheno)]BF4+4CH3CN;

[0095] Product characterization analysis: The yellow solid product prepared in this experiment was subjected to infrared (IR) spectroscopy. Figure 2 X-ray diffraction (XRD) Figure 3 ) and scanning electron microscope (SEM) Figures 4-8 Through analysis, a more detailed observation of the product's external structure and internal characteristics was conducted, leading to a better understanding of the product.

[0096] Infrared spectroscopy (IR) Figure 2 As a Cu(I) complex, a total of 7 distinct peaks were observed, with the peak at 3056 cm⁻¹. -1 2970cm -1 1693cm -1 1435cm -1 1061cm -1 696cm -1 519cm -1 3056cm -1 2970cm -1 It is the CH stretching vibration peak; 1693 cm⁻¹ -1 This is the stretching vibration peak of C=O. Due to the conjugation of unsaturated bonds with C=O, the absorption peak of C=O shifts to lower wavenumbers; 1435 cm⁻¹ -1 It is the absorption peak of CP on PPh3; 1061 cm⁻¹ -1 The strong absorption peak is BF4 - Characteristic absorption peak; 696 cm⁻¹ -1 It is the absorption peak of the benzene ring and the out-of-plane bending vibration of CH; 519 cm⁻¹ -1 It could be an absorption peak in Cu-P. (Based on infrared spectroscopy) Figure 2 It can be seen that the ligand coordinates with the cuprous ion to synthesize the Cu(I) complex.

[0097] X-ray diffraction (XRD), by Figure 3 It can be seen that the product exhibits a relatively strong diffraction peak at around 2θ = 8°, while some smaller diffraction peaks also appear at other angles, which may be caused by impurities. Figure 3 The highest intensity of the diffraction peak reached about 3400, indicating that the Cu(I) complex has a well-developed crystal structure and high purity.

[0098] Scanning electron microscope (SEM), such as Figures 4-8As shown, Figure 4 This is an image of a Cu(I) complex magnified 20,000 times under a scanning electron microscope; Figure 5 This is an image of a Cu(I) complex magnified 10,000 times under a scanning electron microscope; Figure 6 This is an image of a Cu(I) complex magnified 3000 times under a scanning electron microscope; Figure 7 This is an image of a Cu(I) complex magnified 1000 times under a scanning electron microscope; Figure 8 This is an image of a Cu(I) complex magnified 500 times under a scanning electron microscope;

[0099] As can be seen from the five figures, the Cu(I) complex has a regular shape, resembling needle-like whiskers, with a very smooth surface and a complete crystal morphology. The width of the crystal particles is about 9 micrometers. Some clusters are likely due to incomplete drying of the prepared compound, containing a small amount of moisture. However, these needle-like compounds stack together, forming many voids and increasing the specific surface area. The adsorption and photocatalytic experiments show that it still exhibits good adsorption and photocatalytic effects.

[0100] Photocatalytic degradation experiment of methyl orange by Cu(I) complex.

[0101] The reagents and instruments required for the degradation of methyl orange, and the experimental reagents used in the experiment are listed in Table 2:

[0102] Table 2 Chemicals used in the experiment

[0103]

[0104] Selection of experimental instruments, experimental plan and data processing:

[0105] First, a series of gradient methyl orange solutions were prepared. The optimal absorption wavelength of methyl orange was found online, and a range including the optimal absorption wavelength was selected. A methyl orange solution of a certain concentration was taken, and the optimal wavelength was detected using a UV-Vis spectrophotometer. Then, a standard curve of the methyl orange solution was measured at the optimal wavelength. Next, a methyl orange solution of a certain concentration was selected, and the product was used as a catalyst for adsorption and photocatalysis experiments to determine the optimal time, dosage, and temperature.

[0106] Performance determination of methyl orange, properties of methyl orange:

[0107] This experiment used methyl orange as the degradation target. Methyl orange is formed by the diazotization of p-aminobenzenesulfonic acid followed by coupling with N,N-dimethylaniline. It is alkaline and a commonly used acid-base indicator; it is also an azo dye used in textile printing and dyeing. Its molecular formula is C1. 14 H 14 N3SO3Na, structural formula is:

[0108]

[0109] To determine the maximum absorption wavelength of methyl orange, literature review indicated that the maximum absorption wavelength of methyl orange is 463 nm. Therefore, the required wavelength range was set at 400-500 nm. A 20 mg / L methyl orange solution was prepared, using deionized water as a reference. The solution was placed in a 10 mm glass cuvette and measured using a UV spectrophotometer. The results showed that the maximum absorption wavelength of the methyl orange solution was between 460-470 nm. To determine the optimal wavelength, a second UV spectrophotometer measurement was performed, confirming that the maximum operating wavelength of methyl orange was 463 nm.

[0110] To determine the methyl orange standard curve, the required mass of methyl orange was accurately weighed using an analytical balance, and solutions of methyl orange at concentrations of 5 mg / L, 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, and 30 mg / L were prepared. Deionized water was used as a reference, and the absorbance values ​​of the methyl orange solutions were measured using a 10 mm glass cuvette and a UV spectrophotometer. The correlation coefficient R was then obtained by plotting the equation based on the function. 2 =0.99997, indicating a very good linearity.

[0111] The evaluation method for adsorption and photocatalytic degradation was conducted using a 365nm UV lamp as the light source to irradiate the reactants, with adsorption as a control under natural light. The reaction temperature was set using a constant-temperature water bath. The absorbance values ​​of the methyl orange solution before and after the reaction were measured using a UV spectrophotometer at the maximum absorption wavelength. The adsorption and photodegradation decolorization rates of methyl orange were determined based on the changes in absorbance values ​​before and after the reaction.

[0112] Selection of optimal conditions for the degradation of methyl orange solution under adsorption conditions.

[0113] Selection of the optimal catalyst dosage for methyl orange adsorption: Adsorption reaction: The optimal dosage under adsorption conditions was studied. The catalyst dosage ranged from 10-40 mg, with a gradient of 5 mg. The constant temperature water bath was set to 30℃. 10 mL of a 30 mg / L methyl orange solution with an absorbance of 1.122 was degraded. The initial absorbance of the solution was measured using a UV spectrophotometer. The catalyst was poured into a test tube containing the methyl orange solution and placed under visible light. After 30 minutes, the reaction solution was poured into a 15 mL centrifuge tube, and the centrifuge speed was adjusted to 5000 r / min for 10 min. The absorbance of the methyl orange solution was measured again using a UV spectrophotometer, and the adsorption rate was calculated. The results are as follows: Figure 9 The effect of catalyst dosage on the adsorption of methyl orange is shown in the figure.

[0114] Depend on Figure 9It can be seen that the adsorption rate increases with the increase of catalyst dosage. This is because the contact area between the catalyst and methyl orange increases with the increase of catalyst dosage, resulting in better adsorption. The adsorption rate increases significantly when the catalyst dosage is 15 mg and 30 mg. The increase in adsorption rate is relatively gradual when the catalyst dosage is between 15-25 mg and 30-40 mg. The adsorption rate is highest at 40 mg of catalyst, reaching 84.7%.

[0115] Selection of the optimal time for catalyst adsorption of methyl orange: Adsorption reaction: The optimal time under the adsorption conditions was studied, ranging from 20 to 120 min with a gradient of 20 min. A constant temperature water bath was used at 30℃. 20 mg of catalyst was used to degrade 10 mL of a 30 mg / L methyl orange solution with an absorbance of 1.122. The initial absorbance of the solution was measured using a UV spectrophotometer. The catalyst was then poured into a test tube containing the methyl orange solution and placed under visible light. Samples were taken every 20 min, and the reaction solution was poured into 15 mL centrifuge tubes. The centrifuge speed was set to 5000 r / min and centrifuged for 10 min. The adsorption of the degradation products was measured using a UV spectrophotometer to determine the absorbance value, and the adsorption rate was calculated. The results are as follows: Figure 10 The effect of adsorption time on the adsorption of methyl orange is shown.

[0116] Depend on Figure 10 It can be seen that the adsorption rate of the catalyst for methyl orange solution generally shows an upward trend. The lowest point of 25.8% is reached at 40 min. The adsorption rate gradually increases from 40 to 80 min, with a slight decrease at 100 min, followed by an increase, reaching its highest point of 73.2% at 120 min. Since the fluctuation range of the adsorption rate from 80 to 120 min is not large, it is considered that adsorption reached equilibrium at 80 min.

[0117] Selection of the optimal temperature for catalyst adsorption of methyl orange: Adsorption reaction: To study the optimal temperature under adsorption conditions, 20 mg of each of the seven catalyst products were accurately weighed using an analytical balance and placed in test tubes. Then, 10 mL of a 30 mg / L methyl orange solution with an absorbance of 0.983 was added to each test tube. Appropriate amounts of tap water were poured into a two-well water bath, and the power switch was turned on, setting the temperature to 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, and 80℃ respectively. After the temperature in the two-well water bath stabilized, seven 100 mL test tubes were placed in their respective baths and heated for 30 minutes for adsorption. The reaction solution was then poured into 15 mL centrifuge tubes, and the centrifuge speed was set to 5000 rpm for 10 minutes. The absorbance of the methyl orange solution was then measured using a UV spectrophotometer. The results are as follows: Figure 11 The effect of temperature on the adsorption of methyl orange is shown.

[0118] Depend on Figure 11 It can be seen that the adsorption rate gradually increases with increasing temperature, reaching a maximum of 95.3% at 60℃. This is because, with increasing temperature, the pores in the catalyst expand and enlarge, allowing for the adsorption of more methyl orange per unit area. As the temperature continues to rise, the adsorption rate tends to decrease. This is because excessively high temperatures cause the pores in the catalyst to expand too much, leading to their breakage and reducing the adsorption effect.

[0119] Selection of optimal conditions for catalyst degradation of methyl orange solution under ultraviolet light irradiation.

[0120] Optimal Dosage Selection under UV Irradiation: Photodegradation Reaction: The optimal dosage of catalyst for the catalytic degradation of methyl orange solution under 365 nm UV irradiation was studied. The catalyst dosage ranged from 10-40 mg, with a gradient of 5 mg. A constant temperature water bath was used at 20 °C to degrade 10 mL of 30 mg / L methyl orange solution with an absorbance of 1.010. The initial absorbance of the solution was first measured using a UV spectrophotometer. Then, the catalyst was poured into a test tube containing methyl orange solution and irradiated under a UV lamp at a wavelength of 365 nm for 30 min. After irradiation, the reaction solution was poured into a 15 mL centrifuge tube, and the centrifuge speed was adjusted to 5000 r / min for 10 min. The absorbance values ​​of different catalyst dosages were then measured using a UV spectrophotometer, and the photocatalytic degradation rate was calculated. The results are as follows: Figure 12 The effect of catalyst dosage on the degradation of methyl orange is shown.

[0121] Depend on Figure 12 It can be seen that as the catalyst dosage gradually increases, the UV photocatalytic degradation rate also gradually increases, reaching a maximum of 87% when the catalyst dosage is 30 mg. This is because as the catalyst dosage increases, the effective surface area of ​​the catalyst also increases, as does the effective surface area exposed to UV light. This increases the number of photogenerated electron-hole pairs, resulting in a greater amount of hydroxyl radicals and highly reactive superoxide ions, thus increasing the photocatalytic degradation rate. However, as the catalyst dosage continues to increase, the degradation rate gradually decreases. When the catalyst dosage exceeds 30 mg, the catalyst begins to stack and aggregate, reducing the effectively utilized surface area and leading to a decrease in the photocatalytic degradation rate.

[0122] Optimal Time Selection under UV Irradiation: Photodegradation Reaction: The optimal time for UV photocatalytic degradation was studied, with an irradiation time range of 20-120 min and a gradient of 20 min. A constant temperature water bath was used, with the temperature set at 20℃. The catalyst dosage was 30 mg, and 10 mL of a 30 mg / L methyl orange solution with an absorbance of 1.116 was used for degradation. The initial absorbance of the solution was measured using a UV spectrophotometer. The catalyst was then poured into a test tube containing the methyl orange solution and placed under a 365 nm UV lamp for irradiation. Every 20 min, the reaction solution was transferred to a 15 mL centrifuge tube, and the centrifuge speed was set to 5000 r / min for 10 min. The absorbance of the degradation products was measured using a UV spectrophotometer, and the photocatalytic degradation rate was calculated. The results are as follows: Figure 13 The effect of light exposure time on the degradation of methyl orange is shown.

[0123] Depend on Figure 13 It can be seen that the photocatalytic degradation rate fluctuates with time. The lowest photocatalytic degradation rate (45.3%) is observed at 60 min, while the highest (82.1%) is observed at 100 min. This is likely related to the effective surface area of ​​the catalyst and the area exposed to ultraviolet light.

[0124] Selection of Optimal Temperature under UV Irradiation: Photodegradation Reaction: The optimal temperature for UV photocatalytic degradation was studied, ranging from 20-80℃ with a temperature gradient of 10℃. The catalyst dosage was 10 mg, and UV irradiation was applied for 30 min. This degraded 10 mL of a 30 mg / L methyl orange solution with an absorbance of 1.010. The initial absorbance of the solution was measured using a UV spectrophotometer. The catalyst was then added to a test tube containing the methyl orange solution and irradiated under a 365 nm UV lamp. Every 30 min, the reaction solution was transferred to a 15 mL centrifuge tube, and the centrifuge was set to 5000 rpm for 10 min. The absorbance of the degradation products was measured using a UV spectrophotometer, and the photocatalytic degradation rate was calculated. The results are as follows: Figure 14 The effect of temperature on the degradation of methyl orange is shown.

[0125] Through adsorption and photocatalytic experiments, this invention analyzed the effects of three factors—catalyst dosage, time, and temperature—on the decolorization rate of methyl orange. The results show that:

[0126] (1) Under the adsorption conditions of constant temperature at 30℃ and standing for 30 min, 10 mL of methyl orange solution with absorbance of 1.122 was degraded, and the optimal amount of catalyst was 40 mg.

[0127] (2) Under the adsorption conditions of constant temperature at 30℃ and catalyst dosage of 20mg, the time to reach adsorption equilibrium for 10mL of methyl orange solution with absorbance of 1.122 was 80min.

[0128] (3) Under the adsorption conditions of 20 mg catalyst and standing for 30 min, 10 mL of methyl orange solution with absorbance of 0.983 was degraded at an optimal temperature of 60 °C.

[0129] (4) Under constant temperature of 20℃ and 365nm ultraviolet light irradiation for 30 min, 10 mL of methyl orange solution with absorbance of 1.010 was degraded. The optimal amount of catalyst was 30 mg.

[0130] (5) Under constant temperature of 20℃ and 365nm ultraviolet light with 30mg catalyst, the highest photocatalytic degradation rate of 10mL methyl orange solution with absorbance of 1.116 was achieved in 100min.

[0131] (6) Under the conditions of 365nm ultraviolet light irradiation with a catalyst dosage of 10mg and standing for 30min, 10mL of methyl orange solution with an absorbance of 1.010 was degraded at an optimal temperature of 70℃.

[0132] The above conclusions indicate that this catalyst has good adsorption and photocatalytic degradation effects on methyl orange.

[0133] The experimental reagents used in the detection of heavy metal ions are shown in Table 3:

[0134] Table 3 Experimental Drugs Select experimental instruments.

[0135] Experimental Procedure and Data Processing: First, using N,N-dimethylformamide as a solvent, a series of product solutions with varying concentrations were prepared. These solutions were then analyzed using a three-dimensional ultraviolet (UV) spectrophotometer to determine the concentration corresponding to the best absorption peak. Next, at this concentration, a mixed solution of seven heavy metal ions was prepared. The product solution and the mixed heavy metal ion solution at these concentrations were then detected using a fluorescence phosphorescence chemiluminescence spectrophotometer to obtain their fluorescence emission peaks. Two heavy metal ions with more pronounced emission peaks were selected, and their detection limits were determined. A series of mixed solutions and product solutions with varying concentrations of the two heavy metal ions were then prepared and analyzed using a fluorescence phosphorescence chemiluminescence spectrophotometer. The emission peaks of these solutions were compared with those of the product solutions to determine the detection limits of the two heavy metal ions.

[0136] Preparation and testing of the product solution; preparation of the product solution:

[0137] (1) Take three portions of the product and use acetonitrile, ethanol and N,N-dimethylformamide as solvents respectively to compare the solubility of the product in the three solvents. The result is that N,N-dimethylformamide is the better solvent.

[0138] (2) Calculate the relative molecular mass (885.12) from the product's molecular formula, and then calculate the required amount of solution (5*10). -3 (mol / l) mass.

[0139] (3) Weigh 0.0885 g of the product using an analytical balance, dissolve it in a beaker using N,N-dimethylformamide as a solvent, and then transfer the solution to a 20 mL volumetric flask using a glass rod. Make up to a final volume of 5 x 10⁻⁶ g. -3 mol / L product solution.

[0140] (4) Using 5*10 -3 The mol / L product solution is the mother liquor. The mother liquor is transferred using a pipette, and the remaining four product solutions (1*10) are prepared in a 10mL volumetric flask. -3 mol / L, 5*10 -4 mol / L, 1*10 -4 mol / L, 5*10 -5 (mol / L).

[0141] Testing of the product solution:

[0142] Five product solutions were analyzed using a three-dimensional ultraviolet analyzer to detect their absorption peaks, and the concentration corresponding to the largest absorption peak was determined. The results are as follows: Figure 15 The ultraviolet absorption peak of the product is shown.

[0143] Depend on Figure 15 As can be seen, the emission peak diagram of each concentration of the product has a relatively high absorption peak (the first peak), which is the instrument's peak; the ultraviolet absorption peak is generally between 200-800 nm; 5*10 -4 mol / L, 1*10 -4 mol / L, 5*10 -5 The emission peak diagram for mol / L shows a second peak, which is the emission peak of the product. Comparison of the graphs shows that it is 5*10⁻⁶. -4 The emission peak of the mol / L product solution is the highest and most obvious.

[0144] Preparation and detection of mixed solutions of heavy metal ions and products.

[0145] Preparation of a mixed solution of heavy metal ions and the product:

[0146] 1) Seven heavy metal salts were selected (cobalt nitrate hexahydrate, chromium(III) nitrate nonahydrate, cadmium nitrate tetrahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, copper nitrate trihydrate, and ferric nitrate(III) nonahydrate).

[0147] 2) Calculate the relative molecular masses of the seven heavy metal salts, and then calculate the required molecular weight for a 5*10⁻⁶ salt configuration. -3The mass of each of the seven heavy metal ion solutions (mol / L) should be measured using an analytical balance.

[0148] 3) Dissolve the heavy metal salt in N,N-dimethylformamide in a beaker, then transfer the solution to a 20mL volumetric flask using a glass rod, and bring the volume up to 5*10. -3 A solution of seven heavy metal ions at a concentration of mol / L.

[0149] 4) Using a 1mL pipette, transfer 1mL of the product solution and one heavy metal ion solution to a 10mL volumetric flask, and dilute to 10mL with N,N-dimethylformamide to obtain 5*10 -4 Prepare a mixed solution of mol / L, and then prepare mixed solutions of the other 6 heavy metal ions according to the same operating procedure.

[0150] Detection of heavy metal ions in mixed solutions of products:

[0151] Seven types of 5*10 -4 A mixed solution of heavy metal ions and products at mol / L with 5*10 -4 The mol / L product solution was analyzed using a fluorescence phosphorescence chemiluminescence spectrophotometer, yielding fluorescence emission peaks for eight samples. Two heavy metal ions with relatively good emission peaks were identified. Results are as follows: Figure 16 The fluorescence emission peaks of the product and heavy metal ions are shown.

[0152] Depend on Figure 16 It can be seen that the incident wavelengths at which the emission intensity of the seven mixed solutions and the product solution is at its maximum are all around 440 nm. Furthermore, the emission peaks of the seven mixed solutions are all higher than those of the product solution, indicating that these seven heavy metal ions have a promoting effect on the fluorescence emission peak of the product at this concentration. It is evident that the mixed solution containing nickel ions has the highest emission peak, followed by the mixed solution containing copper ions. The emission peaks of the remaining five heavy metal ion mixed solutions are not significantly different.

[0153] Preparation of a mixed solution containing nickel and copper ions:

[0154] Through the above Figure 16 It can be seen that the emission peaks of the mixed solution of nickel and copper ions are much higher than those of the product. In order to find the detection limit, the ion concentration is diluted downward.

[0155] (i) First configure 5*10 -3 A mother solution containing nickel ions (mol / L) was prepared, and 1 mL was transferred to a 10 mL volumetric flask using a pipette. The volume was then adjusted to 10 mL with N,N-dimethylformamide to obtain 5*10 mol / L of the solution. -4 A nickel ion-containing solution at mol / L.

[0156] (ii) Then use a pipette to take 1 mL of 5*10-4 A nickel ion-containing solution of mol / L was placed in a 10 mL volumetric flask and diluted to 10 mL with N,N-dimethylformamide to obtain 5*10 mol / L. -5 A nickel ion-containing solution of mol / L. Following this method, 5*10 mol / L can be prepared. -6 mol / L, 5*10 -7 mol / L, 5*10 -8 A nickel ion-containing solution at mol / L.

[0157] Prepare 5*10 using the method described above. -3 mol / L, 5*10 -4 mol / L, 5*10 -5 mol / L, 5*10 -6 mol / L, 5*10 - 7 mol / L, 5*10 -8 A copper ion-containing solution with a concentration of mol / L.

[0158] (iii) Use a pipette to take 5*10 -3 A solution containing nickel ions at a concentration of mol / L and 5*10 -3 1 mL of each mol / L product solution was added to a 10 mL volumetric flask and diluted to 10 mL with N,N-dimethylformamide to obtain 5*10 mol / L solution. -4 A mixed solution containing nickel ions at a concentration of mol / L.

[0159] (iv) Use a pipette to take 5*10 -4 A solution containing nickel ions at a concentration of mol / L and 5*10 -3 1 mL of each mol / L product solution was added to a 10 mL volumetric flask and diluted to 10 mL with N,N-dimethylformamide to obtain 5*10 mol / L solution. -5 A mixed solution containing nickel ions at a concentration of mol / L.

[0160] (v) Similarly, without changing the concentration of the product solution, only changing the concentration of the nickel ion-containing solution, to prepare 5*10 -4 mol / L, 5*10 -5 mol / L, 5*10 -6 mol / L, 5*10 -7 mol / L, 5*10 -8 mol / L, 5*10 -9 A mixed solution containing nickel ions at a concentration of mol / L.

[0161] (vi) Similarly, prepare 5*10 -4 mol / L, 5*10 -5 mol / L, 5*10 -6mol / L, 5*10 -7 mol / L, 5*10 - 8 mol / L, 5*10 -9 A mixed solution containing copper ions at a concentration of mol / L.

[0162] Detection of mixed solutions containing nickel and copper ions:

[0163] Six mixed solutions containing nickel ions, six mixed solutions containing copper ions, and 5*10 -4 The product solution at mol / L was analyzed using a fluorescence phosphorescent chemiluminescence spectrophotometer. The results are as follows: Figure 17 Fluorescence emission peaks of nickel ions and their products Figure 18 The fluorescence emission peaks of copper ions and the product are shown in the diagram.

[0164] Depend on Figure 17 It can be seen that, from top to bottom, the highest peak corresponds to a nickel ion concentration of 5*10. -4 mol / L, the second is 5*10 - 8 mol / L, the third is 5*10 -5 mol / L, the fourth is 5*10 -6 mol / L, the fifth is 5*10 -9 mol / L, the sixth is 5*10 -7 mol / L, the last line is the emission peak of the black product solution, and you can see the green 5*10 -7 The peak values ​​corresponding to the nickel ion concentration of mol / L are basically consistent with those of the black product. Therefore, the detection limit for nickel ions in the product is determined to be 5*10 mol / L. -7 mol / L.

[0165] Depend on Figure 18 It can be seen that, from top to bottom, the highest peak corresponds to a copper ion concentration of 5*10. -4 mol / L, the second is 5*10 - 5 mol / L, the third black peak is the product's emission peak curve, and the fourth is 5*10. -8 mol / L, the fifth is 5*10 -7 mol / L, the sixth is 5*10 -6 mol / L, the last one is 5*10 -9 mol / L. It can be seen that the peak portion of the product is similar to 5*10. -8 The peak values ​​for copper ion concentrations (mol / L) show good agreement. Therefore, the detection limit for copper ions in the product is determined to be 5*10⁻⁶. -8 mol / L.

[0166] By analyzing product solutions of different concentrations using a three-dimensional ultraviolet spectrometer, the concentration corresponding to the highest emission peak of the product was determined. At this concentration, product solutions containing different heavy metal ions were detected using fluorescence, and two heavy metal ions (nickel ions and copper ions) with high sensitivity were identified. Then, fluorescence detection was performed on product solutions containing different concentrations of nickel ions and copper ions, and the detection limits for the two heavy metal ions were found to be 5*10⁻⁶. -7 mol / L and 5*10 -8 mol / L.

[0167] In summary, this experiment employed a substitution method, using copper powder, copper oxide, tetrafluoroboric acid, triphenylphosphine (PPh3), and 1,10-o-phenanthroline-5,6-dione (pheno) as raw materials and acetonitrile as solvent to prepare a Cu(I) complex. Methyl orange was used as a model of organic pollutants, and the effects of different dosages, times, and temperatures on the degradation effect were investigated using a single-factor method. Simultaneously, its ability to detect heavy metal ions was analyzed. Finally, the Cu(I) complex was characterized by XRD, IR, and SEM analysis. The above experiments lead to the conclusion that:

[0168] Infrared analysis revealed absorption peaks formed by the nitrogen- and phosphine-coordinated copper salts, indicating the successful formation of the Cu(I) complex.

[0169] XRD characterization shows that the diffraction peak intensity reaches a maximum of about 3400, indicating that the Cu(I) complex has a well-developed crystal structure and high purity.

[0170] SEM analysis showed that the Cu(I) complex had a smooth surface and formed a good crystal structure with a width of about 9 micrometers. The stacking phenomenon formed many pores, which increased the specific surface area. Adsorption and photocatalysis experiments showed that the catalyst had good adsorption and photocatalytic effects.

[0171] The degradation experiments of methyl orange show that under adsorption conditions, the optimal catalyst dosage is 40 mg, the optimal adsorption time is 80 min, and the optimal temperature is 60℃; under ultraviolet light irradiation conditions, the optimal catalyst dosage is 30 mg, the optimal irradiation time is 100 min, and the optimal temperature is 70℃.

[0172] The heavy metal ion detection experiments show that, under the conditions of a three-way ultraviolet spectrometer and a fluorescence phosphorescence chemiluminescence spectrophotometer, the detection limits for nickel and copper heavy metal ions are 5*10⁻⁶. -7 mol / L and 5*10 -8 mol / L.

[0173] The novel and complex valence bonds and spatial configurations of Cu(I) coordination compounds have not only promoted the continuous development of structural chemistry and theoretical chemistry, but their unique physical and chemical properties have also attracted widespread attention in modern scientific research and production. In particular, some Cu(I) complexes with special optical, electrical, and magnetic functions have become research hotspots in chemical engineering, materials science, and optical physics. This study on the photocatalytic degradation of methyl orange and the detection of heavy metal ions utilizes its unique optical and electrical properties. Experimental results show that the phosphorescent probe method has good results in the detection of heavy metal ions, allowing for the detection of a wider range of substances. Given the good adsorption, photocatalytic, and detection effects of this Cu(I) complex, it can be applied to wastewater treatment and environmental pollution control.

[0174] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention and within the spirit and principles of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A Cu(I) complex, characterized in that, This Cu(I) complex is used for the degradation of organic dye wastewater and the detection of heavy metal ions. Its molecular formula is [Cu(PPh3)2(pheno)]BF4, and its structural formula is: 。 2. A method for preparing a Cu(I) complex, characterized in that, This method is used to prepare the Cu(I) complex described in claim 1. The method employs a substitution method, reacting triphenylphosphine PPh3 and 1,10-o-diazaphenanthroline-5,6-dione ligands with the copper salt [Cu(CH3CN)4]BF4 to prepare the Cu(I) complex; specifically... include: S1: Add acetonitrile, copper tetrafluoroborate tetraacetonitrile [Cu(CH3CN)4]BF4 and triphenylphosphine PPh3 to a flask, then add 1,10-o-diazaphenanthroline-5,6-dione, and stir the mixture thoroughly on a magnetic stirrer. S2: Add diethyl ether until a precipitate forms, let stand, filter, and air dry to obtain the Cu(I) complex.

3. The method for preparing the Cu(I) complex according to claim 2, characterized in that, In step S1, the molar ratio of [Cu(CH3CN)4]BF4:triphenylphosphine:1,10-o-diazaphenanthroline-5,6-dione is 1:2:

1.

4. The process for the preparation of Cu(I) complexes according to claim 2, characterized in that, In step S1, tetrafluoroborate tetraacetonitrile [Cu(CH3CN)4]BF4, triphenylphosphine PPh3, and 1,10-o-diazaphenanthroline-5,6-dione, i.e., pheno, are reacted; the reaction formula is as follows: 。 5. The use of Cu(I) complex in the degradation of organic dye wastewater, characterized in that, This application is achieved using the Cu(I) complex described in claim 1, and the application uses methyl orange solution as the degradation target.

6. The use of the Cu(I) complex according to claim 5 for the degradation of organic dye wastewater, characterized in that, Under adsorption conditions of constant temperature at 30℃ and standing for 30 min, the mass-to-volume ratio of Cu(I) complex to methyl orange solution was 4:1; or, The degradation of methyl orange solution was carried out at a constant temperature of 30℃ with a Cu(I) complex catalyst to methyl orange solution mass-to-volume ratio of 2:1, and the adsorption equilibrium time was 80 min; or, The adsorption conditions were: Cu(I) complex catalyst to methyl orange solution at a mass-to-volume ratio of 2:1, standing for 30 min, and temperature of 60℃.

7. The use of the Cu(I) complex according to claim 5 for the degradation of organic dye wastewater, characterized in that, Under constant temperature of 20℃ and UV irradiation for 30 min, the methyl orange solution was degraded with a Cu(I) complex to methyl orange solution mass-to-volume ratio of 3:1; or, The methyl orange solution was degraded by incubation at a constant temperature of 20℃. The mass-to-volume ratio of the Cu(I) complex to the methyl orange solution was 3:

1. Under ultraviolet light irradiation, the highest photocatalytic degradation rate was achieved in 100 minutes. The methyl orange solution was degraded by a Cu(I) complex to methyl orange solution mass-volume ratio of 1:1, allowed to stand for 30 min, and then subjected to ultraviolet light at a temperature of 70℃.

8. Use of a Cu(I) complex for the detection of heavy metal ions, characterized in that, The application is implemented using the Cu(I) complex described in claim 1, and the detected heavy metal ions are nickel ions and copper ions.

9. The application of the Cu(I) complex according to claim 8 in the detection of heavy metal ions, characterized in that, Fluorescence detection was performed on product solutions containing different concentrations of nickel and copper ions, and the detection limits for the two heavy metal ions were found to be 5*10⁻⁶. -7 mol / L and 5*10 -8 mol / L.

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