Phosphorescent cu(i) complexes, methods of making and use in detecting aromatic amine compounds

Abstract

The application discloses a phosphorescent Cu(I) complex, a preparation method and application thereof in detection of aromatic amine compounds. The phosphorescent Cu(I) ligand material is prepared from an organic phosphorus material 1,4-bis(diphenylphosphino)butane, a copper salt CuI and 1,10-phenanthroline-5,6-dione as raw materials. The phosphorescent Cu(I) ligand material prepared by the application has good adsorption and photodegradation effects on a methyl orange solution, and can be used for photocatalytic degradation of pollutants in water. Meanwhile, the phosphorescent Cu(I) complex has good detection effect on the aromatic amine compounds, and fluorescence detection can still reflect spectral changes under the condition that the concentration of the aromatic amine is 5x10 ‑9 mol / L.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of water pollution treatment, in particular to a phosphorescent Cu(I) complex, a preparation method and application thereof in detecting aromatic amine compounds. BACKGROUND

[0002] Sewage treatment is a key point in environmental problems, and the treatment of urban sewage and industrial sewage consumes a huge amount of capital. Chemical methods are important methods for water pollution treatment, and photocatalytic degradation of organic pollutants in sewage is a hot spot in the field of water treatment research. The existing photocatalytic materials have high cost, and the treatment efficiency has room for improvement. Therefore, it is of great significance to develop new materials with low cost and high treatment efficiency for water pollution treatment.

[0003] In addition, aromatic amine compounds are a kind of dye toxic and harmful to the human body. Long-term contact with the human body, the dye is easily absorbed by the skin and diffused in the human body. These dyes may undergo reduction reaction to decompose carcinogenic aromatic amines through normal metabolic reactions of the human body, and change the DNA structure of the human body through the activation of the human body, causing human disease and inducing cancer, and the incubation period can be as long as 20 years. At present, the methods for detecting the content of carcinogenic aromatic amines mainly include thin layer chromatography (TLC), high performance liquid chromatography-mass spectrometry (HPLC-MS), high performance liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS / MS), and spectrophotometry. These detection methods have problems such as long detection time, complex process, high detection cost, etc. Therefore, it is of great significance to develop a new detection method for aromatic amine compounds. SUMMARY

[0004] The present application provides a phosphorescent Cu(I) complex, a preparation method and application thereof in detecting aromatic amine compounds to solve the above technical problems.

[0005] In a first aspect, the present application provides a preparation method of a phosphorescent Cu(I) complex, which is realized by using the following technical scheme.

[0006] The preparation method of the phosphorescent Cu(I) complex comprises the following steps:

[0007] S1. Adding acetonitrile to CuI powder, the mass-volume ratio of CuI and acetonitrile is 0.019-0.030 g / 4-6 ml, and fully stirring;

[0008] S2. Adding 1,4-(bis diphenylphosphine) butane to the mixture obtained in step S1, the molar ratio of 1,4-(bis diphenylphosphine) butane to CuI is 1:1, and fully reacting to obtain a turbid liquid containing a powdery precipitate;

[0009] S3. Adding 1,10-phenanthroline-5,6-dione to the turbid liquid obtained in step S2, the molar ratio of 1,10-phenanthroline-5,6-dione to CuI is 1:1, and continuing to stir to obtain a turbid liquid containing a powdery precipitate;

[0010] S4. Adding excess ether to the turbid liquid obtained in step S3 to completely precipitate the product, filtering and drying the filtered product at a low temperature to obtain the phosphorescent Cu(I) complex.

[0011] Further, in step S1, the stirring time is 0.5-1h.

[0012] Further, in step S2, the sufficient reaction time is 1-2h.

[0013] Further, in step S3, the stirring time is 1-2h.

[0014] Further, in step S4, the ether is added at room temperature, and the stirring time is 5min-30min.

[0015] In a second aspect, the present application provides a phosphorescent Cu(I) complex, which is realized by the following technical scheme.

[0016] A phosphorescent Cu(I) complex prepared by the above preparation method.

[0017] In a third aspect, the present application provides a first use of the phosphorescent Cu(I) complex, which is realized by the following technical scheme.

[0018] Application of the above phosphorescent Cu(I) complex in photocatalytic degradation of pollutants.

[0019] Further, the mass ratio of the phosphorescent Cu(I) complex to methyl orange is 250:1.

[0020] Further, the reaction time of the phosphorescent Cu(I) complex adsorbing methyl orange is 30-120min, and the reaction temperature is 25-40℃; under light conditions, the reaction time of the phosphorescent Cu(I) complex degrading methyl orange is 0.5-2.5h, and the reaction temperature is 35-50℃.

[0021] In a fourth aspect, the present application provides a second use of the phosphorescent Cu(I) complex, which is realized by the following technical scheme.

[0022] Application of the above phosphorescent Cu(I) complex in detecting aromatic amine compounds.

[0023] Further, the aromatic amine compounds include p-methoxyaniline, 4-bromoaniline, p-iodoaniline, and 4-chloroaniline.

[0024] The present application has the following beneficial effects.

[0025] (1) The phosphorescent Cu(I) complex of the present application has low cost, small toxicity, easy development, and good product performance;

[0026] (2) The preparation method of the phosphorescent Cu(I) complex of the present application is simple, which only needs to dissolve the reactants in a suitable solvent, and the target product can be obtained by self-assembly in the solution;

[0027] (3) The phosphorescent Cu(I) complex prepared by the present application has good performance in the experiment of photocatalytic degradation of pollutants. From the photocatalysis and degradation experiment results, it can be known that the optimal dosage of the product is 25 mg, the optimal reaction time is 2.5 h, the optimal reaction temperature is 30℃, and the optimal decolorization effect reaches 84.92%. And under normal temperature conditions, a high adsorption effect can be achieved after 30 min of reaction, and the photodegradation of the product is enhanced to a certain extent by ultraviolet light. The phosphorescent Cu(I) complex of the present application is expected to be put into the field of wastewater treatment;

[0028] (4) The phosphorescent Cu(I) complex prepared by the present application has good detection effect on four kinds of aromatic amines, and the aromatic amines can still be detected at very low concentration, and the detection limit concentration is about 5x10 -9 mol / L. The phosphorescent Cu(I) complex of the present application is expected to be put into the field of aromatic amine detection. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a real object diagram of the phosphorescent Cu(I) ligand prepared by the present application;

[0030] Figure 2 is an infrared absorption spectrum diagram of the phosphorescent Cu(I) ligand prepared by the present application;

[0031] Figure 3 is a scanning electron microscope analysis diagram of the phosphorescent Cu(I) ligand prepared by the present application;

[0032] Figure 4 is an X-ray diffraction diagram of the phosphorescent Cu(I) ligand prepared by the present application;

[0033] Figure 5 is an ultraviolet absorption spectrum diagram of the phosphorescent Cu(I) ligand prepared by the present application;

[0034] Figure 6 is a comparison diagram of the adsorption rate of the phosphorescent Cu(I) ligand of the present application on methyl orange with different dosages (without ultraviolet light);

[0035] Figure 7 is a comparison diagram of the adsorption rate of the phosphorescent Cu(I) ligand of the present application on methyl orange under different reaction times (without ultraviolet light).

[0036] Figure 8 The phosphorescent Cu(I) ligand of the present application is compared with the adsorption rate of methyl orange at different reaction temperatures (without ultraviolet light conditions);

[0037] Figure 9 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction times (ultraviolet light conditions);

[0038] Figure 10 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction times (ultraviolet light conditions);

[0039] Figure 11 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction temperatures (ultraviolet light conditions);

[0040] Figure 12 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction times (ultraviolet light conditions); -4 mol / L of the product solution; B1. The concentration of 4-chloroaniline in the mixed solution is 1×10 -4 mol / L; B2. The concentration of 4-chloroaniline in the mixed solution is 5×10 -5 mol / L; B3. The concentration of 4-chloroaniline in the mixed solution is 1×10 -5 mol / L; B4. The concentration of 4-chloroaniline in the mixed solution is 5×10 -6 mol / L);

[0041] Figure 13 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction times (ultraviolet light conditions); -4 mol / L of the product solution; B5. The concentration of 4-chloroaniline in the mixed solution is 5×10 -7 mol / L; B6. The concentration of 4-chloroaniline in the mixed solution is 5×10 -8 mol / L; B7. The concentration of 4-chloroaniline in the mixed solution is 5×10 -9 mol / L);

[0042] Figure 14 The phosphorescent Cu(I) ligand of the present application is compared with the decolorization rate of methyl orange at different reaction times (ultraviolet light conditions); -4 mol / L of the product solution; C1. The concentration of 4-chloroaniline in the mixed solution is 1×10 -4 mol / L; C2. The concentration of 4-chloroaniline in the mixed solution is 5×10 -5 mol / L; C3. The concentration of 4-chloroaniline in the mixed solution is 1×10-5 mol / L; C4. The concentration of p-methoxyaniline in the mixture is 5 × 10 mol / L; -6 mol / L);

[0043] Figure 15 These are fluorescence spectra of mixtures of p-methoxyaniline at different concentrations and a certain concentration of the product (where A is a concentration of 5 × 10⁻⁶). -4 The product solution was prepared at a concentration of mol / L; C5. The concentration of p-methoxyaniline in the mixture was 5 × 10⁻⁶ mol / L. -7 mol / L; C6. The concentration of p-methoxyaniline in the mixed solution is 5 × 10⁻⁶ mol / L; -8 mol / L; C7. The concentration of p-methoxyaniline in the mixed solution is 5 × 10⁻⁶ mol / L; -9 mol / L);

[0044] Figure 16 These are fluorescence spectra of mixtures of 4-bromoaniline at different concentrations and the product at a fixed concentration according to the present invention (where A is a concentration of 5 × 10⁻⁶). -4 The product solution was prepared at a concentration of mol / L; D1. The concentration of 4-bromoaniline in the mixture was 1×10⁻⁶. -4 mol / L; D2. The concentration of 4-bromoaniline in the mixed solution is 5 × 10⁻⁶ mol / L; -5 mol / L; D3. The concentration of 4-bromoaniline in the mixture is 1×10⁻⁶ mol / L; -5 mol / L; D4. The concentration of 4-bromoaniline in the mixture is 5 × 10⁻⁶ mol / L; -6 mol / L);

[0045] Figure 17 These are fluorescence spectra of mixtures of 4-bromoaniline at different concentrations and the product at a fixed concentration according to the present invention (where A is a concentration of 5 × 10⁻⁶). -4 The product solution was prepared at a concentration of mol / L; D5. The concentration of 4-bromoaniline in the mixture was 5 × 10⁻⁶ mol / L. -7 mol / L; D6. The concentration of 4-bromoaniline in the mixture is 5 × 10⁻⁶ mol / L; -8 mol / L; D7. The concentration of 4-bromoaniline in the mixed solution is 5 × 10⁻⁶ mol / L; -9 mol / L);

[0046] Figure 18 These are fluorescence spectra of mixtures of p-iodoaniline at different concentrations and a product at a fixed concentration according to the present invention (where A is a concentration of 5 × 10⁻⁶). -4 The product solution was prepared at a concentration of mol / L; E1. The concentration of p-iodoaniline in the mixture was 1×10⁻⁶. -4 mol / L; E2. The concentration of p-iodoaniline in the mixed solution is 5 × 10 mol / L; -5 mol / L; E3. The concentration of p-iodoaniline in the mixed solution is 1×10 mol / L; -5 mol / L; E4. The concentration of p-iodoaniline in the mixed solution is 5 × 10⁻⁶ mol / L; -6mol / L);

[0047] Figure 19 is the fluorescence spectrum of the mixed solution of different concentrations of p-iodoaniline and a constant concentration of product (wherein A. The concentration of p-iodoaniline is 5 x 10 -4 mol / L of product solution; E5. The concentration of p-iodoaniline in the mixed solution is 5 x 10 -7 mol / L; E6. The concentration of p-iodoaniline in the mixed solution is 5 x 10 -8 mol / L; E7. The concentration of p-iodoaniline in the mixed solution is 5 x 10 -9 mol / L). DETAILED DESCRIPTION

[0048] The application will be further described below in conjunction with the drawings and examples.

[0049] I. Experimental instruments and reagents

[0050] In this application, acetonitrile is used as the solvent, and CuI, 1,4-bis(diphenylphosphino) butane and 1,10-phenanthroline-5,6-dione are used as raw materials to prepare phosphorescent Cu(I) complexes (hereinafter referred to as "product"). Methyl orange solution is used as the degradation object, and the single factor method is used to analyze the optimal reaction time, temperature, dosage, etc. A certain concentration of product solution and different concentrations of four kinds of aromatic amine compounds solution are prepared, and the two solutions are mixed for fluorescence detection, and the effect of the product on the aromatic amine compounds is analyzed according to the change of the spectrum.

[0051] The experimental instruments used in the experiment are shown in Table 1.

[0052] The characterization instruments used in the experiment are shown in Table 2.

[0053] The reagents used in the experiment are shown in Table 3.

[0054] Table 1 Experimental instruments

[0055]

[0056] Table 2 Experimental characterization instruments

[0057]

[0058] Table 3 Chemical reagents used in the experiment

[0059]

[0060] II. Experimental methods and results

[0061] 1. Preparation of Cu(I) ligand

[0062] The experimental steps are as follows:

[0063] (1) Accurately weigh CuI (0.0015 mol, 0.287 g) solid into a round bottom flask, add 10 ml acetonitrile into the flask and stir on a constant temperature heating magnetic stirrer.

[0064] (2) Accurately weigh 1,4-(bis diphenylphosphino) butane (0.0015 mol, 0.6397 g) into the flask and allow it to react completely to obtain a turbid liquid containing white powder precipitate. The reaction rate can be accelerated by heating appropriately, but the temperature should not be too high.

[0065] (3) Accurately weigh 1,10-phenanthroline-5,6-dione (0.0015 mol, 0.3153 g) into the flask and continue to stir to obtain a turbid liquid containing light yellow powder precipitate. After the reaction is complete, turn off the heating magnetic stirrer.

[0066] (4) Add excess ether into the flask to completely precipitate the product. Dry the product obtained by filtration by heating slightly and store in a sample tube. The product is shown in Figure 1 .

[0067] 2. Characterization of phosphorescent Cu(I) complex product

[0068] The product solid is subjected to infrared, scanning electron microscopy (SEM), X-ray diffraction (XRD) and ultraviolet absorption spectrum detection and analysis.

[0069] The infrared spectrum is shown in Figure 2 . In the infrared absorption spectrum of the product, the peaks at 3218 cm -1 , 3053 cm -1 , 2929 cm -1 are caused by the stretching motion of hydrogen-containing groups X-H, X = C, N, O. 1631 cm -1 is the frequency or combination of the out-of-plane bending vibration of the benzene derivative C-H, and can also be the stretching vibration of the double bond. 1435 cm -1 is the C-P bond stretching vibration absorption peak. 1121 cm -1 , 1021 cm -1 are I - . 694 cm -1 is the peak of the out-of-plane deformation vibration absorption peak of the benzene ring C-H. 513 cm -1 is the absorption peak of the Cu-P bond stretching vibration.

[0070] The scanning electron microscopy results are shown in Figure 3 . It can be seen that the product is irregular granular, with some particles clustered together, which can be due to the absorption of moisture in the air during storage of the product. The rough and porous structure of the surface of the product particles makes it have good adsorption and catalytic performance.

[0071] X-ray diffraction results are as follows Figure 4 As shown in the figure, ①, ②, and ③ correspond to distinct and good diffraction peaks at 7.398°, 12.603°, and 14.653°, respectively, confirming successful coordination between the reactants based on the molecular formula. These three diffraction peaks are due to the different coordination ratios between the reaction product of CuI and 1,4-bis(diphenylphosphine)butane and 1,10-phenanthroline-5,6-dione. Diffraction peaks appearing at other angles belong to reactants, reaction derivatives, and other impurities.

[0072] Several concentrations of product solutions were analyzed using a three-dimensional ultraviolet analyzer. The ultraviolet absorption characteristics of the products are as follows: Figure 5 In the diagram, A1 is 1×10. -3 The product solution has a concentration of mol / L, and A2 is 2 × 10⁻⁶. -4 The product solution has a concentration of mol / L, and A3 is 5 × 10⁻⁶. -4 The product solution has a concentration of mol / L, and A4 is 5 × 10⁻⁶. -5 A product solution of mol / L. From Figure 5 It can be seen that the product has two distinct absorption bands, at 112 nm and 331 nm, respectively. The absorption band at 331 nm belongs to the Cu(I) ligand of the target product. The concentration is 5 × 10⁻⁶. -4 The product absorption peak at mol / L is more obvious and smooth, so this concentration was chosen as the product concentration for subsequent fluorescence detection.

[0073] 3. Detection of photocatalytic performance of phosphorescent Cu(I) complex products

[0074] The single-factor method was used to investigate the adsorption and degradation performance of Cu(I) complex products on methyl orange solution under different temperatures, product amounts, reaction times, and the presence or absence of ultraviolet light.

[0075] Evaluation methods for photocatalytic degradation

[0076] The ultraviolet light from a UV-Vis spectrophotometer was used as the light source, and the reaction temperature was room temperature. The absorbance of the methyl orange solution before and after the reaction was measured using a UV-Vis spectrophotometer at the maximum wavelength (464 nm). The degradation and decolorization rate of the methyl orange was calculated based on the change in absorbance before and after the reaction, using the following formula:

[0077]

[0078] In the formula: Ao: absorbance value before reaction; At: absorbance value after reaction.

[0079] The photocatalytic reaction experiment was divided into two parts: 1. the adsorption process under no ultraviolet light conditions; 2. the photodegradation process under ultraviolet light conditions.

[0080] 3.1 Determination of optimal conditions under no light

[0081] Determination of the optimum amount of product under the condition of no light: 5 mg, 10 mg, 15 mg, 20 mg, 25 mg and 30 mg of product were accurately weighed in six test tubes, and 10 ml of 10 mg / L methyl orange solution was added to each test tube. The test tubes were shaken to mix the contents uniformly, and then left to stand for 1 h. The absorbance of the filtrate obtained by filtering the mixture was determined using a UV spectrophotometer. The room temperature was 25°C at this time.

[0082] The experimental results are shown in Table 1, and it can be seen from Table 1 that, as the amount of product increased, the adsorption rate gradually increased and reached a maximum at 25 mg. The adsorption rate at 15 mg was close to the maximum, and the adsorption rate at 20 mg decreased slightly, which might have been caused by the fact that the product was not mixed uniformly or the product particles were too large to contact the methyl orange solution sufficiently. The adsorption rates at 25 mg and 30 mg were not much different from that at 15 mg, which indicated that, in this experiment, the effect of the amount of product on the adsorption rate of the methyl orange solution increased first and then stabilized. The optimum amount of product was 25 mg, and the maximum adsorption rate was 77.59%. Figure 6 Figure 6 Determination of the optimum time under the condition of no light: 15 mg of product was accurately weighed in eight test tubes, and 10 ml of 10 mg / L methyl orange solution was added to each test tube. The test tubes were shaken to mix the contents uniformly, and then left to stand to start timing. One test tube was taken out every 15 min to determine the absorbance of the filtrate. The room temperature was 17°C at this time.

[0083] The experimental results are shown in Table 2, and it can be seen from Table 2 that, as the reaction time increased, the adsorption rate increased first and then showed a fluctuating trend, and reached a maximum at 105 min. Although the adsorption rate fluctuated between 30 min and 105 min, the overall adsorption rate gradually increased and then decreased after 105 min. Therefore, the optimum reaction time was 105 min, and the maximum adsorption rate was 79.45%.

[0084] Determination of the optimum temperature under the condition of no light: 15 mg of product was accurately weighed in five test tubes, and 10 ml of 10 mg / L methyl orange solution was added to each test tube. The test tubes were shaken to mix the contents uniformly, and then placed in a constant-temperature water bath at 30°C, 40°C, 50°C, 60°C and 70°C, respectively. The test tubes were taken out after 15 min and filtered to determine the absorbance of the filtrate. Figure 7 Figure 7 The experimental results are shown in Table 3, and it can be seen from Table 3 that, as the temperature increased, the adsorption rate increased first and then showed a fluctuating trend, and reached a maximum at 60°C. The adsorption rate at 50°C was close to the maximum, and the adsorption rate at 70°C decreased slightly, which might have been caused by the fact that the product was not mixed uniformly or the product particles were too large to contact the methyl orange solution sufficiently. The adsorption rates at 30°C and 40°C were not much different from that at 50°C, which indicated that, in this experiment, the effect of the temperature on the adsorption rate of the methyl orange solution increased first and then stabilized. The optimum temperature was 60°C, and the maximum adsorption rate was 79.45%.

[0085] The experimental results are shown in Table 3, and it can be seen from Table 3 that, as the temperature increased, the adsorption rate increased first and then showed a fluctuating trend, and reached a maximum at 60°C. The adsorption rate at 50°C was close to the maximum, and the adsorption rate at 70°C decreased slightly, which might have been caused by the fact that the product was not mixed uniformly or the product particles were too large to contact the methyl orange solution sufficiently. The adsorption rates at 30°C and 40°C were not much different from that at 50°C, which indicated that, in this experiment, the effect of the temperature on the adsorption rate of the methyl orange solution increased first and then stabilized. The optimum temperature was 60°C, and the maximum adsorption rate was 79.45%.

[0086] The experimental results are shown in Table 3, and it can be seen from Table 3 that, as the temperature increased, the adsorption rate increased first and then showed a fluctuating trend, and reached a maximum at 60°C. The adsorption rate at 50°C was close to the maximum, and the adsorption rate at 70°C decreased slightly, which might have been caused by the fact that the product was not mixed uniformly or the product particles were too large to contact the methyl orange solution sufficiently. The adsorption rates at 30°C and 40°C were not much different from that at 50°C, which indicated that, in this experiment, the effect of the temperature on the adsorption rate of the methyl orange solution increased first and then stabilized. The optimum temperature was 60°C, and the maximum adsorption rate was 79.45%. Figure 8 Figure 8 ​​​It can be seen that with the increase of ambient temperature, the adsorption rate gradually decreases as a whole. Since the temperature in the laboratory reaches 25℃, the initial temperature of the experiment is 30℃. According to the experimental data of the optimal dosage and optimal time under the control of no light conditions, the adsorption rate below 30℃ is lower than 80%, so it can be determined that the optimal reaction temperature is 30℃, and the optimal adsorption rate is 82.72%.

[0087] 3.2 Determination of optimal conditions under ultraviolet light

[0088] Under ultraviolet light, the optimal dosage was determined by accurately weighing 10 mg, 15 mg, 20 mg, 25 mg and 30 mg of the product in 5 test tubes, and adding 10 mg / L of methyl orange solution 10 ml to each test tube. Shake the test tubes to mix them evenly, and let them stand for 30 min to reach adsorption equilibrium. Place the test tubes under the ultraviolet light for 80 min, take out the test tubes and filter them, and measure the absorbance of the filtrate. At this time, the room temperature is 20℃.

[0089] The experimental results are shown in Table 1. Figure 9 As can be seen from Table 1, with the gradual increase of the dosage of the product, the decolorization rate first increases, reaches a maximum at 25 mg, and then decreases. Comparing the data of different product dosages under the control of no light conditions, the decolorization rate improves to a certain extent, indicating that ultraviolet light promotes the degradation of methyl orange under this condition. The optimal dosage is 25 mg, and the maximum decolorization rate is 83.38%. Figure 9 Figure 6 Under ultraviolet light, the optimal time was determined by accurately weighing 5 portions of 20 mg of the product in 5 test tubes, and adding 10 mg / L of methyl orange solution 10 ml to each test tube. Shake the test tubes to mix them evenly, and let them stand for 30 min to reach adsorption equilibrium. Place the test tubes under the ultraviolet light, and every 0.5 h, take out one test tube and filter it, and measure the absorbance of the filtrate. At this time, the room temperature is 25.8℃.

[0090] The experimental results are shown in Table 2. As can be seen from Table 2, with the increase of reaction time, the decolorization rate shows a fluctuating trend, and reaches a maximum at 2.5 h. It can be seen that although the data is fluctuating, the decolorization rate is at a relatively high level, and the difference is not large, which may be caused by the error of uneven mixing of the product and the solution. Comparing the data of different reaction times under the control of no light conditions, the decolorization rate is generally higher than the adsorption rate, indicating that ultraviolet light promotes the degradation of methyl orange under this condition. The optimal reaction time is 2.5 h, and the maximum decolorization rate is 84.92%.

[0091] Figure 10 Figure 10

[0092] ​​​To determine the optimal temperature under ultraviolet light, accurately weigh 20 mg of the product into a test tube using an analytical balance, and add 10 ml of 10 mg / L methyl orange solution. Shake the test tube to mix thoroughly and let it stand for 30 min to reach adsorption equilibrium. Place the test tube in a 30°C constant temperature water bath and irradiate with ultraviolet light for 30 min. Remove the test tube, filter, and measure the absorbance of the filtrate. The room temperature at this point is 25°C. Increase the water bath temperature by 10°C and repeat the above steps until the water bath temperature reaches 70°C.

[0093] Experimental results are as follows Figure 11 As shown, by Figure 11 It can be seen that as the reaction temperature increases, the decolorization initially increases and then gradually decreases, before increasing again at 70℃. (Control) Figure 8 Data from different reaction temperatures under no-light conditions showed that at 30℃ and 40℃, the decolorization rate under UV irradiation was lower than the adsorption rate under no-light conditions, indicating that UV irradiation weakened the adsorption effect at these temperatures. However, between 50 and 70℃, the decolorization rate under UV irradiation was greater than the adsorption rate under no-light conditions, indicating that UV irradiation promoted the degradation of methyl orange within this temperature range. The optimal reaction temperature was 40℃, with a maximum decolorization rate of 77.2%.

[0094] 4. Application of phosphorescent Cu(I) complexes in the detection of aromatic amines

[0095] The fluorescence detection was performed in two steps, with the first detection concentration being 5 × 10⁻⁶. -4 A product solution with a concentration of 5 × 10⁻⁶ mol / L (the solvent of the product solution is DMF). -4 The product solution with a concentration of mol / L and four concentrations of 1×10 -4 mol / L, 5×10 -5 mol / L, 1×10 -5 mol / L, 5×10 -6 A mixed solution of aromatic amines at a concentration of 5 × 10⁻⁶ mol / L. The concentration was measured a second time. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The product solution with a concentration of mol / L and four concentrations of 5×10 -7 mol / L, 5×10 -8 mol / L, 5×10 -9 A mixed solution of aromatic amines in mol / L concentrations. The excitation wavelength for detection was 350 nm. The four aromatic amines were: p-methoxyaniline, 4-bromoaniline, p-iodoaniline, and 4-chloroaniline.

[0096] 4.1. Reaction of phosphorescent Cu(I) complex with 4-chloroaniline

[0097] First test: Concentration 5×10 -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L.-4 A mixture of the product at a concentration of mol / L and 4-chloroaniline, with 4-chloroaniline concentrations of 1×10⁻⁶. -4 mol / L, 5×10 -5 mol / L, 1×10 -5 mol / L, 5×10 - 6 mol / L, the detection results are as follows Figure 12 As shown.

[0098] Depend on Figure 12 The first fluorescence detection showed that the fluorescence intensity of the mixture of 4-chloroaniline and the product was greater than that of the single product, indicating that 4-chloroaniline enhances the fluorescence intensity of the product. As the concentration of 4-chloroaniline gradually decreased, the fluorescence intensity of the mixture first decreased and then increased. This demonstrates that the product has a good detection effect on 4-chloroaniline.

[0099] Second test: Concentration 5×10 -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The concentrations of the product (mol / L) and 4-chloroaniline were 5 × 10⁻⁶ mol / L and 5 × 10⁻⁶ mol / L, respectively. -7 mol / L, 5×10 -8 mol / L, 5×10 -9 The test results for the mixed solution of mol / L are as follows: Figure 13 As shown.

[0100] Depend on Figure 13 It can be seen that, in the second fluorescence detection, the fluorescence intensity of the mixture of 4-chloroaniline and the product was still greater than that of the single product. Furthermore, the fluorescence intensity decreased as the concentration of 4-chloroaniline decreased. At a 4-chloroaniline concentration of 5 × 10⁻⁶, the fluorescence intensity also decreased. -9 At a concentration of 5 × 10⁻⁶ mol / L, the fluorescence intensity of the mixed solution is very close to that of the single product solution. - 9 mol / L can be used as the detection limit for the product detection of 4-chloroaniline.

[0101] 4.2. Reaction of phosphorescent Cu(I) complex with p-methoxyaniline

[0102] The initial test showed a concentration of 5 × 10⁻⁶. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The concentrations of the product and p-methoxyaniline were 1×10 mol / L and 10 mol / L, respectively. -4 mol / L, 5×10 -5 mol / L, 1×10 -5 mol / L, 5×10 -6 The test results for the mixed solution of mol / L are as follows:Figure 14 .

[0103] Depend on Figure 14 It can be seen that the fluorescence intensity of the mixture of p-methoxyaniline and the product is greater than that of the single product solution. As the concentration of p-methoxyaniline decreases, the fluorescence intensity of the mixture gradually approaches that of the single product. This indicates that the product has a good detection effect on p-methoxyaniline, and that p-methoxyaniline enhances the fluorescence intensity of the product.

[0104] The second test showed a concentration of 5 × 10⁻⁶. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The concentrations of the product and p-methoxyaniline were 5 × 10 mol / L and 5 × 10 mol / L, respectively. -7 mol / L, 5×10 -8 mol / L, 5×10 -9 The test results for the mixed solution of mol / L are as follows: Figure 15 .

[0105] Depend on Figure 15 It can be seen that the fluorescence intensity of the mixture of p-methoxyaniline and the product is greater than that of the single product solution. As the concentration of p-methoxyaniline decreases, the fluorescence intensity of the mixture first increases and then decreases. At a p-methoxyaniline concentration of 5 × 10⁻⁶, the fluorescence intensity of the mixture is... -9 At a concentration of 5 × 10⁻⁶ mol / L, the fluorescence intensity of the mixed solution is close to that of the single product solution. -9 mol / L can be used as the detection limit for the product detection of p-methoxyaniline.

[0106] 4.3. Reaction of phosphorescent Cu(I) complex with 4-bromoaniline

[0107] The initial test showed a concentration of 5 × 10⁻⁶. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The concentrations of the product (mol / L) and 4-bromoaniline were 1×10⁻⁶. -4 mol / L, 5×10 -5 mol / L, 1×10 -5 mol / L, 5×10 -6 The test results for the mixed solution of mol / L are as follows: Figure 16 .

[0108] Depend on Figure 16 It can be seen that the fluorescence intensity of the mixture of 4-bromoaniline and the product is greater than that of the single product solution. As the concentration of 4-bromoaniline gradually decreases, the fluorescence intensity of the mixture first decreases and then increases, and reaches 1×10⁻⁶. -4 mol / L, 1×10 -5 mol / L, 5×10 -6The fluorescence intensity of the mixed solution at the three mol / L concentrations showed significant changes. This indicates that the product has a good detection effect on 4-bromoaniline. However, the detection limit cannot be determined when the concentration of 4-bromoaniline is too high. It is necessary to further reduce the concentration of 4-bromoaniline before conducting detection.

[0109] The second test showed a concentration of 5 × 10⁻⁶. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The concentrations of the product (mol / L) and 4-bromoaniline were 5 × 10⁻⁶ mol / L and 5 × 10⁻⁶ mol / L, respectively. -7 mol / L, 5×10 -8 mol / L, 5×10 -9 The test results for the mixed solution of mol / L are as follows: Figure 17 .

[0110] Depend on Figure 17 It can be seen that the fluorescence intensity of the mixture of 4-bromoaniline and the product is greater than that of the single product solution. As the concentration of 4-bromoaniline gradually decreases, the fluorescence intensity of the mixture first increases and then decreases, reaching a maximum at a concentration of 5 × 10⁻⁶. - 9 At a concentration of mol / L, the fluorescence intensity is almost the same as that of the single product solution. This indicates that 4-bromoaniline at this concentration cannot be detected, and the detection limit for 4-bromoaniline is between 5 × 10⁻⁶ mol / L. -8 -5×10 -9 Between mol / L.

[0111] 4.4. Reaction of phosphorescent Cu(I) complex with p-iodoaniline

[0112] The initial test showed a concentration of 5 × 10⁻⁶. -4 The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The product concentration and the p-iodoaniline concentration were 1×10 mol / L, respectively. -4 mol / L, 5×10 -5 mol / L, 1×10 -5 mol / L, 5×10 -6 The test results for the mixed solution of mol / L are as follows: Figure 18 .

[0113] Depend on Figure 18 It can be seen that the fluorescence intensity of the mixture of p-iodoaniline and the product is greater than that of the single product solution. As the concentration of p-iodoaniline gradually decreases, the fluorescence intensity of the mixture continuously increases. This indicates that the product has a good detection effect on p-iodoaniline, but the concentration of p-iodoaniline is still too high to determine the detection limit. The concentration of p-iodoaniline needs to be further reduced before detection can be performed.

[0114] The second test showed a concentration of 5 × 10⁻⁶. -4The product solution has a concentration of 5 × 10⁻⁶ mol / L. -4 The product concentration and the p-iodoaniline concentration were 5 × 10 mol / L, respectively. -7 mol / L, 5×10 -8 mol / L, 5×10 -9 The test results for the mixed solution of mol / L are as follows: Figure 19 .

[0115] Depend on Figure 19 It can be seen that the fluorescence intensity of the mixture gradually decreases as the concentration of p-iodoaniline gradually decreases. At a p-iodoaniline concentration of 5 × 10⁻⁶, the fluorescence intensity of the mixture also gradually decreases. -9 At a concentration of mol / L, the fluorescence intensity of the mixed solution is lower than that of the single-product solution. This may be because the solution has been left for a longer period after preparation, causing some product to precipitate out, resulting in a lower fluorescence intensity in the mixed solution compared to the single-product solution. This indicates that the detection limit for iodoaniline is between 5 × 10⁻⁶ mol / L. -8 -5×10 -9 Between mol / L.

[0116] The embodiments described herein are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape, and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. The application of a phosphorescent Cu(I) complex in the detection of aromatic amine compounds, characterized in that: The aromatic amine compound is p-methoxyaniline, 4-bromoaniline, p-iodoaniline, or 4-chloroaniline, and the preparation method of the phosphorescent Cu(I) complex includes the following steps: S1. Add acetonitrile to CuI powder, with a mass-to-volume ratio of CuI to acetonitrile of 0.019-0.030 g / 4-6 ml, and stir thoroughly; S2. Add 1,4-(bisdiphenylphosphine)butane to the mixture obtained in step S1. The molar ratio of 1,4-(bisdiphenylphosphine)butane to CuI is 1:

1. After the reaction is complete, a turbid liquid containing powdery precipitate is obtained. S3. Add 1,10-phenanthroline-5,6-dione to the turbid liquid obtained in step S2. The molar ratio of 1,10-phenanthroline-5,6-dione to CuI is 1:

1. Continue stirring to obtain a turbid liquid containing powdery precipitate. S4. Add excess diethyl ether to the turbid liquid obtained in step S3 to allow the product to precipitate completely. Filter the product and then dry it with a gentle heat to obtain the phosphorescent Cu(I) complex.

2. The application according to claim 1, characterized in that: In step S1, the stirring time is 0.5-1 hour.

3. The application according to claim 1, characterized in that: In step S2, the reaction time is 1-2 hours.

4. The application according to claim 1, characterized in that: In step S3, the stirring time is 1-2 hours.

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