A method for synthesizing a phenylacetylene copper composite photocatalyst in situ in one step and application thereof
By preparing a cyanophenylacetylene copper/phenylacetylene copper homo-heterojunction composite photocatalyst, the problem of high photogenerated charge recombination rate was solved, achieving efficient degradation of water pollutants, especially diclofenac, which has broad-spectrum degradation ability and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGDONG UNIV OF TECH
- Filing Date
- 2025-11-13
- Publication Date
- 2026-07-03
AI Technical Summary
Existing photocatalysts exhibit high photo-generated charge recombination rates under visible light, which limits their catalytic performance and makes it difficult to effectively degrade non-steroidal pollutants such as diclofenac in water.
By preparing a homo-heterojunction composite photocatalyst of cyanophenylacetylene copper/phenylacetylene copper (CN-PhC2Cu/PhC2Cu), a tight interface is formed by utilizing van der Waals forces. The cyano group acts as a strong electron-withdrawing group to regulate the interface electron density, promoting exciton dissociation and photogenerated electron delocalization. A one-step in-situ synthesis method is adopted to simplify the process.
The photocatalytic performance was significantly improved. The composite material increased the degradation rate of diclofenac by 5.6 times under visible light, and it can degrade a variety of water pollutants in a broad spectrum. It also has good stability and adaptability.
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Figure CN121338822B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalytic materials technology, specifically relating to a homogeneous-heterojunction composite photocatalyst based on copper phenylacetylene, particularly to a copper phenylacetylene-based homogeneous-heterojunction composite photocatalyst that promotes exciton dissociation and photogenerated electron delocalization through cyanoylation of functional groups, as well as its simple one-step in-situ synthesis preparation process and its application in the degradation of pollutants in water. Background Technology
[0002] Diclofenac (DCF), a commonly used nonsteroidal anti-inflammatory drug, accumulates continuously in water bodies due to its difficulty in biodegradation, posing a threat to ecosystems and human health. Photocatalysis technology has attracted widespread attention due to its highly efficient ability to degrade pollutants, especially semiconductor photocatalysis, which can utilize solar energy to degrade pollutants and reduce heavy metals in water bodies, and is considered one of the green and efficient environmental remediation methods. However, existing catalysts generally suffer from problems such as high photogenerated charge recombination rates and low visible light utilization rates.
[0003] Copper phenylacetylene (PhC₂Cu), an organometallic semiconductor, possesses a band gap of approximately 2.3 eV, can be excited by visible light, and exhibits a relatively negative conduction band potential, demonstrating strong reduction capabilities and promising application potential in photocatalysis. However, it still faces the bottleneck of rapid charge carrier recombination, limiting further improvements in its catalytic performance.
[0004] Homo-heterojunctions, due to their similar constituent unit structures, can form a tight interface structure, which is conducive to efficient charge transfer and is an effective strategy for suppressing photogenerated electron-hole recombination. This invention synthesizes a heterojunction of cyanophenylacetylene copper (CN-PhC2Cu) and phenylacetylene copper (PhC2Cu) via a simple one-step in-situ method. This method is simple, operates under mild conditions, and the prepared heterojunction effectively promotes charge separation, significantly improving photocatalytic performance. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention adjusts the ratio of PhC2Cu to CN-PhC2Cu to prepare a high-performance CN-PhC2Cu / PhC2Cu homojunction composite photocatalyst with high visible light response and low photogenerated carrier recombination efficiency. Under visible light irradiation, it can achieve efficient degradation of non-steroidal substances such as dichlorophenolic acid and other water pollutants.
[0006] To achieve the above-mentioned technical objectives, the present invention adopts the following technical solution:
[0007] This invention first provides a cyanophenylacetylene copper / phenylacetylene copper (CN-PhC2Cu / PhC2Cu) homo-heterojunction composite photocatalyst. In the photocatalyst, CN-PhC2Cu and PhC2Cu form a tight interface through van der Waals forces. The conduction band energy level of CN-PhC2Cu is lower than that of PhC2Cu. The cyano group (-CN) acts as a strong electron-withdrawing group to regulate the interfacial electron density and promote exciton dissociation and photogenerated electron delocalization.
[0008] Specifically, in the photocatalyst, the molar ratio of CN-PhC2Cu to PhC2Cu is 0.15~0.90:1, preferably 0.70~0.80:1.
[0009] Secondly, this invention also provides a method for one-step in-situ synthesis of cyanophenylacetylene copper / phenylacetylene copper (CN-PhC2Cu / PhC2Cu) homo-heterojunction composite photocatalysts, comprising the following steps:
[0010] 1) At room temperature, copper chloride dihydrate (CuCl2・2H2O) is placed in the first solvent and added while stirring until completely dissolved; then triethylamine, 4-ethynylbenzonitrile (cyano source) and phenylacetylene (PhC2H) are added in sequence, and stirred for 5~15 min until the system is homogeneous to obtain mixed solution one;
[0011] 2) Heat and stir the mixture obtained in step 1) for 5 to 35 minutes. After the reaction is completed, an orange-yellow flocculent precipitate (CN-PhC2Cu / PhC2Cu homojunction precursor) is generated.
[0012] 3) After the reaction in step 2), the product was naturally cooled to room temperature. It was allowed to stand for 10-30 minutes, then centrifuged, the solid was collected, washed, dried, ground and sieved to obtain CN-PhC2Cu / PhC2Cu homojunction composite photocatalyst (i.e. xCNPC photocatalyst (x is 15, 30, 45, 60, 75, 90)).
[0013] Furthermore, in step 1), the first solvent is methanol, ethanol, or a mixture of methanol and ethanol; preferably, the first solvent is methanol.
[0014] Furthermore, in step 1), the mass ratio of copper chloride dihydrate to the volume ratio of the first solvent is (0.365~0.730) g : (40~80) mL.
[0015] More preferably, the mass ratio of copper chloride dihydrate to the volume ratio of the first solvent in step 1) is 0.365 g: 40 mL.
[0016] Further, in step 1), the volume ratio of the first solvent, triethylamine, and phenylacetylene is (40~80):(1.12~2.24):(0.024~0.235).
[0017] Furthermore, in step 1), the mass ratio of 4-ethynylbenzonitrile to phenylacetylene is (0.04~0.24) g : (0.024~0.235) mL.
[0018] Furthermore, in step 1), the ratio of the volume of the first solvent, the volume of triethylamine, the mass of 4-ethynylbenzonitrile, and the volume of phenylacetylene is (40~80) mL : (1.12~2.24) mL : (0.04~0.24) g : (0.024~0.235) mL.
[0019] More preferably, in step 1), the ratio of the volume of the first solvent, the volume of triethylamine, the mass of 4-ethynylbenzonitrile, and the volume of phenylacetylene is 40 mL: 1.12 mL: 0.204 g: 0.059 mL.
[0020] Furthermore, the heating and stirring reaction in step 2) is carried out at a temperature of 60~70℃; more preferably, the heating and stirring reaction in step 2) is carried out at a temperature of 65℃.
[0021] More preferably, the heating and stirring reaction time in step 2) is 5~30 min or 25~35 min.
[0022] More preferably, the heating and stirring reaction time in step 2) is 30 min.
[0023] Furthermore, during the heating and stirring reaction described in step 2), the stirring rate is 200~300 rpm to ensure that the mixture is heated evenly and to avoid component agglomeration caused by localized reactions.
[0024] Furthermore, in step 3), the centrifugation speed is 8000~12000 rpm and the centrifugation time is 5~10 min.
[0025] More preferably, in step 3), the centrifugation speed is 10,000 rpm and the centrifugation time is 8 min.
[0026] Furthermore, the washing operation described in step 3) is as follows: first, the solid product is ultrasonically dispersed with deionized water for 5 minutes and then centrifuged to discard the supernatant; then, the solid product is ultrasonically dispersed with anhydrous ethanol for 5 minutes and then centrifuged; a total of 2-3 washes with water and 1-2 washes with anhydrous ethanol are performed to remove residual unreacted raw materials and impurities.
[0027] Furthermore, the drying temperature in step 3) is 60~70℃, and the drying time is 6~10h.
[0028] More preferably, the drying temperature in step 3) is 65°C and the drying time is 8 hours.
[0029] Specifically, in step 3), the grinding is done using an agate mortar and pestle, and the sieve is passed through a 100-mesh sieve. After sieving, the powder that passes through the sieve is collected to ensure that the catalyst particle size is uniform and to improve the mass transfer efficiency in the photocatalytic reaction.
[0030] Furthermore, the present invention also provides a high-performance CN-PhC2Cu / PhC2Cu homojunction composite photocatalyst with high visible light response and low photogenerated carrier recombination efficiency prepared by the above method.
[0031] Furthermore, based on a general inventive concept, the present invention also provides the application of the CN-PhC2Cu / PhC2Cu homo-heterojunction composite photocatalyst in the photocatalytic degradation of water pollutants.
[0032] Specifically, the pollutants are one or more of the following: nonsteroidal pollutants, bisphenol pollutants, fluoroquinolone pollutants, and sulfonamide compounds.
[0033] Preferably, the contaminant is one or more of sulfadiazine, ofloxacin, enrofloxacin, sulfisoxazole, ciprofloxacin, fluoxetine, and diclofenac.
[0034] Furthermore, based on a general inventive concept, the present invention also provides a method for photocatalytic degradation of water pollutants using the aforementioned CN-PhC2Cu / PhC2Cu homo-heterojunction composite photocatalyst, comprising the following steps:
[0035] The CN-PhC2Cu / PhC2Cu homogeneous-heterojunction composite photocatalyst was mixed with a water pollutant solution to obtain a mixed solution. An LED lamp was used as a light source to irradiate the mixed solution for 30-80 minutes to carry out a photocatalytic reaction, and the content of water pollutants in the mixed solution was measured.
[0036] Preferably, before irradiating the mixed solution, the mixed solution is first subjected to a dark reaction under dark conditions for 10-30 minutes.
[0037] Specifically, the ratio of the amount of CN-PhC2Cu / PhC2Cu homogeneous-heterojunction composite photocatalyst to the water pollutant solution is (5~45) mg: (30~60) mL.
[0038] Specifically, the concentration of the pollutant solution in the water is 5~30 mg / L.
[0039] Specifically, the LED light power is 7~12W, preferably 9W.
[0040] Specifically, the light source used in the photocatalytic reaction is a blue LED lamp (wavelength 455-460nm, illuminance 6.2mW·cm²). -2 ).
[0041] Specifically, the water body refers to tap water, seawater, river water, industrial wastewater, or river water, etc.
[0042] Specifically, the water pollutants are one or more of the following: sulfadiazine, ofloxacin, enrofloxacin, sulfisoxazole, ciprofloxacin, fluoxetine, and diclofenac.
[0043] Compared with the prior art, the advantages of the present invention are:
[0044] 1. Simple preparation process: The raw material mixing and reaction are completed by one-step in-situ synthesis, without the need for multi-step compounding or high-temperature treatment. The reaction temperature is only 60~70℃ and the time is 25~35min. The process is simple and low cost.
[0045] 2. Carrier modulation: The steady-state fluorescence intensity decreases, and the steady-state fluorescence spectrum can reflect the recombination of photogenerated carriers. PhC2Cu has a strong fluorescence peak at 467 nm, CN-PhC2Cu has a strong fluorescence peak at 530 nm, while 75CNPC shows a significant decrease in fluorescence intensity at 534 nm (e.g., Figure 4 (As shown). This further demonstrates that the composite system can effectively suppress the recombination of photogenerated electron-hole pairs and improve quantum efficiency.
[0046] 3. Alteration of photocatalytic activity: By varying the ratio of 4-ethynylbenzonitrile and phenylacetylene, the composite material xCNPC (x = 15, 30, 45, 60, 75, 90) was used in visible light degradation experiments on diclofenac (e.g., ...). Figure 5 As shown in the figure, phenylacetylene copper and cyanophenylacetylene copper exhibit limited photocatalytic activity in the visible light range, while the degradation rate of the composite material 75CNPC is increased by 5.6 times and 2.2 times compared with PhC2Cu and CN-PhC2Cu, respectively. This indicates that by combining the two materials, the easy recombination of electrons in phenylacetylene copper can be effectively overcome, and the recombination of photogenerated electrons can be suppressed by the electron transfer characteristics of the heterojunction, thereby improving the degradation efficiency.
[0047] 4. Reliable Application: To assess the applicability of 75CNPC, different contaminants (such as...) were evaluated. Figure 6 ), under conditions of coexistence of different ions (such as Figure 7 , 8 ) and under different pH conditions (e.g. Figure 9 The activity of the 75CNPC composite photocatalytic system was evaluated. Results showed that the 75CNPC composite photocatalytic material could achieve efficient degradation of diclofenac and other pollutants in various systems. Attached Figure Description
[0048] Figure 1 The images provided are SEM images of CN-PhC2Cu, PhC2Cu, and 75CNPC, TEM images of 75CNPC, and EDS mapping images of C, N, and Cu elements obtained in Comparative Examples 1, 2, and 1 of this application.
[0049] Figure 2 The X-ray diffraction (XRD) pattern of the CN-PhC2Cu / PhC2Cu composite photocatalyst prepared in Example 1 of this application;
[0050] Figure 3 The UV-Vis diffuse reflectance (UV-VisDRS) spectrum of the CN-PhC2Cu / PhC2Cu composite photocatalyst prepared in Example 1 of this application is shown.
[0051] Figure 4 The photoluminescence (PL) spectrum of the CN-PhC2Cu / PhC2Cu composite photocatalyst prepared in Example 1 of this application is shown.
[0052] Figure 5 The graph shows the photocatalytic degradation efficiency of diclofenac removal by CN-PhC2Cu / PhC2Cu (75wt%) prepared in Example 1, CN-PhC2Cu / PhC2Cu (15wt%) in Example 2, CN-PhC2Cu / PhC2Cu (30wt%) in Example 3, CN-PhC2Cu / PhC2Cu (45wt%) in Example 4, CN-PhC2Cu / PhC2Cu (60wt%) in Example 5, CN-PhC2Cu / PhC2Cu (75wt%) in Example 6, CN-PhC2Cu / PhC2Cu (90wt%) in Example 7, PhC2Cu in Comparative Example 1, and CN-PhC2Cu in Comparative Example 2.
[0053] Figure 6 This is a graph showing the degradation rate of different drugs sulfadiazine, ofloxacin, enrofloxacin, sulfamethoxazole, ciprofloxacin, fluoxetine and diclofenac by the CN-PhC2Cu / PhC2Cu composite catalyst prepared in Example 1 of this application.
[0054] Figure 7 The graph shows the removal efficiency of the CN-PhC2Cu / PhC2Cu composite catalyst prepared in Example 1 of this application for the degradation of diclofenac in a coexisting cation water body.
[0055] Figure 8 The graph shows the removal efficiency of the CN-PhC2Cu / PhC2Cu composite catalyst prepared in Example 1 of this application for the degradation of diclofenac in coexisting anion water.
[0056] Figure 9 The graph shows the removal efficiency of the CN-PhC2Cu / PhC2Cu composite catalyst prepared in Example 1 of this application for the degradation of diclofenac under different pH conditions (pH=3, 5, 7, 9, 11). Detailed Implementation
[0057] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.
[0058] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the instruments and equipment used in the following examples are commercially available conventional instruments and equipment; unless otherwise specified, the reagents, raw materials, etc. used in the following examples are conventional commercial products and can be obtained through commercial channels.
[0059] In the following examples, room temperature or normal temperature refers to 25±5℃.
[0060] In the following examples and comparative examples, all raw materials used were commercially available analytical grade reagents (copper chloride dihydrate: purity ≥99%; 4-acetylenebenzonitrile: purity ≥98%; phenylacetylene: purity ≥98%; methanol, triethylamine: purity ≥99.5%).
[0061] Example 1: Preparation of 75CNPC homo-heterojunction composite photocatalyst
[0062] (1) At room temperature, weigh 0.365 g of copper chloride dihydrate and add it to 40 mL of methanol. Stir magnetically until completely dissolved. Add 1.12 mL of triethylamine and continue stirring for 5 min. Then add 0.204 g of 4-ethynylbenzonitrile and 0.059 mL of phenylacetylene and stir for 10 min to obtain mixture one.
[0063] (2) Place the mixture in a 65℃ constant temperature water bath and stir for 30 min to generate an orange-yellow flocculent precipitate;
[0064] (3) After the reaction in step (2) is completed, the product is naturally cooled to room temperature, left to stand for 10 min, and then centrifuged (10000 rpm, 5 min) to collect the solid. Wash once with deionized water and twice with anhydrous ethanol. Dry under vacuum at 65℃ for 8 h, grind, and pass through a 100-mesh sieve to obtain 75CNPC photocatalyst (of which the mass ratio of CN-PhC2Cu / PhC2Cu is 75wt%).
[0065] Example 2: Preparation of 15CNPC homo-heterojunction composite photocatalyst
[0066] The difference from Example 1 is that in step (1), the amount of 4-ethynylbenzonitrile added is 0.04 g and the amount of phenylacetylene added is 0.201 mL. The remaining steps are the same as in Example 1, and finally 15CNPC photocatalyst is obtained.
[0067] Example 3: Preparation of 30CNPC homo-heterojunction composite photocatalyst
[0068] The difference from Example 1 is that in step (1), the amount of 4-ethynylbenzonitrile added is 0.08g and the amount of phenylacetylene added is 0.071mL. The remaining steps are the same as in Example 1, and the 30CNPC photocatalyst is finally obtained.
[0069] Example 4: Preparation of 45CNPC homo-heterojunction composite photocatalyst
[0070] The difference from Example 1 is that in step (1), the amount of 4-ethynylbenzonitrile added is 0.12g and the amount of phenylacetylene added is 0.130mL. The remaining steps are the same as in Example 1, and finally 45CNPC photocatalyst is obtained.
[0071] Example 5: Preparation of 60CNPC homo-heterojunction composite photocatalyst
[0072] The difference from Example 1 is that in step (1), the amount of 4-ethynylbenzonitrile added is 0.16g and the amount of phenylacetylene added is 0.094mL. The remaining steps are the same as in Example 1, and finally 60CNPC photocatalyst is obtained.
[0073] Example 6: Preparation of 90CNPC homo-heterojunction composite photocatalyst
[0074] The difference from Example 1 is that in step (1), the amount of 4-ethynylbenzonitrile added is 0.24g and the amount of phenylacetylene added is 0.024mL. The remaining steps are the same as in Example 1, and finally 90CNPC photocatalyst is obtained.
[0075] Comparative Example 1: Preparation of CN-PhC2Cu photocatalyst
[0076] The difference from Example 1 is that only 0.272g of 4-ethynylbenzonitrile is added in step (1), and phenylacetylene is not added. The remaining steps are the same as in Example 1, and CN-PhC2Cu photocatalyst is obtained.
[0077] Comparative Example 2: Preparation of PhC2Cu photocatalyst
[0078] The difference from Example 1 is that only 0.235 mL of phenylacetylene is added in step (1), and 4-acetylenylbenzonitrile is not added. The remaining steps are the same as in Example 1, and pure PhC2Cu photocatalyst is obtained.
[0079] Application Experiment 1: Performance Testing of CN-PhC2Cu / PhC2Cu Composite Photocatalyst System
[0080] The degradation of diclofenac (DCF) under visible light was tested using the products of Examples 1-6 and Comparative Examples 1 and 2. The optimal catalytic mechanism was revealed through active free radical detection and kinetic calculations. The specific steps are as follows:
[0081] 1. Prepare a 10 mg / L DCF solution and take 50 mL of it into a 50 mL beaker, then add 20 mg of photocatalyst.
[0082] 2. Under dark conditions, the dark reaction is carried out for 30 minutes to reach adsorption-desorption equilibrium, and then a 9W blue LED lamp (455-460nm, 6.2mW·cm⁻¹) is used. -2 The sample was irradiated for 60 minutes as a reaction light source, and 1 mL was taken every 10 minutes. After filtration through a 0.45 μm filter membrane, the DCF concentration was determined by high performance liquid chromatography.
[0083] 3. According to η=(1-C t The removal rate of DCF by the CN-PhC2Cu / PhC2Cu composite photocatalyst was calculated using (C0)×100%, where C0 is the initial concentration of DCF, and C... t This represents the remaining concentration.
[0084] 4. Repeat steps 1 to 3 above to determine the degradation rate of DCF by CN-PhC2Cu / PhC2Cu (15 wt%), CN-PhC2Cu / PhC2Cu (30 wt%), CN-PhC2Cu / PhC2Cu (45 wt%), CN-PhC2Cu / PhC2Cu (60 wt%), CN-PhC2Cu / PhC2Cu (75 wt%), CN-PhC2Cu / PhC2Cu (90 wt%) prepared in Examples 2, 3, 4, 5, and 6, as well as CN-PhC2Cu and PhC2Cu prepared in Comparative Examples 1 and 2.
[0085] The obtained data is summarized and processed to obtain Figure 5 .
[0086] Test results are as follows Figure 5 As shown, a 75wt% formulation is optimal, achieving a DCF degradation rate of 88.10% within 60 minutes, with kapp = 0.033 min. -1 , is PhC2Cu (0.005min -16.6 times that of CN-PhC2Cu (0.010 min) -1 The degradation rates were 3.2 times higher at 90 wt% / 60 wt% / 45 wt% / 30 wt% / 15 wt% of 63.76% / 57.30% / 61.83% / 63.83% / 64.27%, respectively, with kapp decreasing to 0.0107 / 0.0103 / 0.0116 / 0.0108 / 0.0112 min. -1 Therefore, it can be concluded that the 75CNPC (75wt%) of Example 1 of the present invention has better photocatalytic performance.
[0087] Application Experiment 2: Broad-spectrum Degradation Test of Different Pollutants
[0088] To verify the degradation ability of the 75CNPC photocatalyst described in Example 1 for different types of water pollutants and dyes, sulfadiazine, ofloxacin, enrofloxacin, sulfisoxazole, ciprofloxacin, fluoxetine, and diclofenac were selected as target pollutants, and the specific steps were the same as in Application Experiment 1.
[0089] The test results are as follows Figure 6 As shown, after 60 minutes, 75CNPC achieved a degradation rate of over 70% for all seven pollutants. Among them, sulfadiazine (SIZ) had the highest degradation rate at 93.14%, enrofloxacin (ENR) at 87.84%, and diclofenac (DCF) at 87.30%. Ciprofloxacin (CIP), fluoxetine (FLX), ofloxacin (OFX), and sulfamethoxazole had the next highest degradation rates at 85.08%, 82.19%, 80.28%, and 73.28%, respectively.
[0090] Application Experiment 3: Anti-ion Interference Performance Test
[0091] The DCF degradation performance of the 75CNPC photocatalyst described in Example 1 was tested under different ion interference conditions. The specific steps were the same as in Application Experiment 1, except that the test groups were HA (humic acid) and Ca... 2+ Fe 3+ Cu 2+ NH4 + Cl - SO4 2- NO3 - CO3 2- HCO3 - (like Figure 7 , 8 (as shown) and a control group without added interfering ions.
[0092] Cations, anions, and DOM in natural water may affect the photodegradation of DCF in the 75CNPC system. For example... Figure 7As shown, metal cations (Ca²⁺, Cu²⁺, and Fe³⁺) are present, among which Fe³⁺ exhibits a significant inhibitory effect (degradation rate drops to 85.38%, kapp decreases by 31%), while Ca²⁺, Cu²⁺, etc., have little effect. This inhibition may be because metal ions such as Fe³⁺ compete for photogenerated electrons, stealing electrons required for the formation of •O₂⁻, thereby weakening the radical-based oxidation pathway.
[0093] As a representative of aquatic DOM, the presence of HA severely inhibited the removal of DCF by 75CNPC (the degradation rate dropped to 83.34%, and kapp decreased by 34%). This may be due to the combined effects of HA in filtering incident light, scavenging active species (RS), and blocking adsorption sites on the catalyst surface.
[0094] Furthermore, the presence of SO4²⁻, Cl⁻, HCO3⁻, and NO3⁻ also affected the photodegradation of DCF. Among them, SO4²⁻ (degradation rate 82.50%) and HCO3⁻ (degradation rate 88.29%) showed the most significant inhibitory effects, while NO3⁻ had almost no effect. This phenomenon can be attributed to the competitive adsorption of SO4²⁻, Cl⁻, HCO3⁻, and DCF at the catalyst active sites, especially SO4²⁻, which is strongly adsorbed on the surface due to its high charge density; at the same time, HCO3⁻, as a highly efficient quencher of •OH, significantly reduced the dominant oxidation effect of hydroxyl radicals.
[0095] Although some coexisting substances inhibited the degradation process to varying degrees, the 60-minute degradation rate of DCF by 75CNPC remained above 82% under all test conditions, indicating that the material has good adaptability and stable catalytic performance in natural water bodies with complex composition.
[0096] Application Experiment 4: pH Adaptability Test
[0097] The performance of the 75CNPC photocatalyst described in Example 1 in degrading DCF under different acid and alkaline conditions was tested. The specific steps were the same as in Application Experiment 1, except that the test groups were pH=(3, 5, 7, 9, 11) and the control group (pH=4.8).
[0098] Test results are as follows Figure 9As shown, 75CNPC exhibits good adaptability to DCF degradation under different initial pH conditions. The degradation efficiency is particularly outstanding under alkaline conditions (pH=9 and 11): at pH=9, the degradation rate reaches 94.69% within 60 min, with an apparent rate constant kapp of 0.0492 min⁻¹; at pH=11, the degradation rate is 93.42%, with kapp of 0.0466 min⁻¹, both demonstrating extremely high photocatalytic activity. Under acidic conditions (pH=3), the degradation rate is 56.77%, with kapp of 0.0119 min⁻¹, which is lower than in alkaline environments, but still shows a certain degradation capacity. Overall, 75CNPC can effectively degrade DCF within a wide pH range (pH 3-11), especially with degradation rates exceeding 93% in the pH 5–11 range, indicating that this material has wide pH applicability and good catalytic stability, making it suitable for practical water purification applications under different acidic and alkaline environments.
[0099] The experimental results of this invention show that the CN-PhC2Cu / PhC2Cu homojunction-heterojunction composite photocatalyst (especially the 75CNPC photocatalyst) of this invention has the best photocatalytic activity and stability, which is significantly better than that of pure component catalysts.
[0100] The foregoing has shown and described the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.
Claims
1. A method for one-step in-situ synthesis of copper cyanophenylacetylene / copper phenylacetylene homojunction composite photocatalysts, characterized in that, Includes the following steps: 1) At room temperature, dissolve copper chloride dihydrate in the first solvent, and then add triethylamine, 4-ethynylbenzonitrile and phenylacetylene in sequence, and stir for 5-15 minutes to obtain mixture one; 2) Heat and stir the mixture obtained in step 1) for 5 to 35 minutes. After the reaction is complete, an orange-yellow flocculent precipitate is generated. 3) After the reaction in step 2), the product was naturally cooled to room temperature, allowed to stand for 10-30 minutes, then centrifuged, the solid was collected, washed, dried, ground and sieved to obtain the cyanophenylacetylene copper / phenylacetylene copper homo-heterojunction composite photocatalyst.
2. The method as described in claim 1, characterized in that, The mass ratio of copper chloride dihydrate to the volume ratio of the first solvent in step 1) is (0.365~0.730) g : (40~80) mL; In step 1), the volume ratio of the first solvent, triethylamine, and phenylacetylene is (40~80):(1.12~2.24):(0.024~0.235). In step 1), the mass ratio of 4-ethynylbenzonitrile to phenylacetylene is (0.04~0.24) g : (0.024~0.235) mL.
3. The method as described in claim 1, characterized in that, The heating and stirring reaction described in step 2) is carried out at a temperature of 60~70℃.
4. The method as described in claim 1, characterized in that, In step 3), the centrifugation speed is 8000~12000 rpm and the centrifugation time is 5~10 min.
5. The method as described in claim 1, characterized in that, The drying temperature in step 3) is 60~70℃, and the drying time is 6~10h.
6. A cyanophenylacetylene copper / phenylacetylene copper homo-heterojunction composite photocatalyst prepared by any one of the methods described in claims 1 to 5.
7. The application of the copper cyanophenylacetylene / copper phenylacetylene homojunction composite photocatalyst of claim 6 in the photocatalytic degradation of water pollutants, characterized in that, The water pollutants are one or more of the following: sulfadiazine, ofloxacin, enrofloxacin, sulfamethoxazole, ciprofloxacin, fluoxetine, and diclofenac.
8. A method for photocatalytic degradation of water pollutants using the copper cyanophenylacetylene / copper phenylacetylene homojunction composite photocatalyst of claim 6, comprising the following steps: The cyanophenylacetylene copper / phenylacetylene copper homogeneous heterojunction composite photocatalyst was mixed with a water pollutant solution to obtain a mixed solution. An LED lamp was used as a light source to irradiate the mixed solution for 30-80 minutes to carry out a photocatalytic reaction, and the content of water pollutants in the mixed solution was measured.
9. The method according to claim 8, characterized in that, The ratio of the amount of the cyanophenylacetylene copper / phenylacetylene copper homogeneous heterojunction composite photocatalyst to the water pollutant solution is (5~45) mg: (30~60) mL; The concentration of the pollutant solution in the water body is 5~30 mg / L; The water pollutants are one or more of the following: sulfadiazine, ofloxacin, enrofloxacin, sulfamethoxazole, ciprofloxacin, fluoxetine, and diclofenac.