Study On Preparation Of CMPs And The Adsorption Behavior Of PPCPs

With the development of modern society,the use of pharmaceuticals and personal care products has increased dramatically and these products have become more and more prevalent in our life.Due to their strong persistence and difficulty in degradation,these products often remain in wastewater treatment plants and are subsequently discharged into natural water bodies,posing serious threats to aquatic organisms and even endangering human health.Antiviral drugs and sulfonamide antibiotics are widely used in human medicine and livestock breeding due to their excellent antiviral and antibacterial properties.However,the overuse and improper handling of these products have caused various types of pollution,which pose potential risks to human health.Therefore,it is necessary to develop efficient methods to remove these pollutants.Adsorption is widely used for the removal of pollutants due to its convenient operation and low cost,and the key to the adsorption process is to develop efficient adsorbents.Conjugated microporous polymers（CMPs）have high specific surface areas,easily modifiable skeleton structures,excellent chemical and thermal stability,and wide availability of raw materials.These characteristics of CMPs show excellent potential for capturing pollutants,and therefore CMPs can be applied as adsorbents for the removal of pharmaceuticals and personal care products.In this study,Buchwald-Hartwig coupling reaction and Sonogashira coupling reaction were used to synthesize corresponding CMPs,and the adsorption of pharmaceuticals and personal care products in water was studied.The influencing factors,including p H value,adsorbent concentration,ion concentration,humic acid,adsorption equilibrium time,initial pollutant concentration,and temperature,were investigated.The adsorption process was explored by adsorption kinetics,adsorption isotherms,and thermodynamics.The regeneration performance of the materials was tested through regeneration experiments,and the adsorption mechanism was discussed by analyzing the properties of the CMPs before and after adsorption.The main research content and results are as follows:（1）BPT-BZ-CMP,a conjugated microporous polymer material,was synthesized through Buchwald-Hartwig coupling reaction catalyzed by palladium under strong alkaline conditions.It was applied as an adsorbent for the adsorption of antiviral drug-famciclovir in water.The morphology of BPT-BZ-CMP was characterized by various techniques,including FT-IR,¹³C solid-state nuclear magnetic resonance,thermal gravimetric analysis,SEM,BET,and Zeta potential detection.In order to study the adsorption behavior of famciclovir on BPT-BZ-CMP,the effects of solution p H,adsorbent concentration and temperature on the maximum adsorption capacity of the adsorbent were investigated.Through the study of adsorption kinetics,adsorption isotherms,and adsorption thermodynamics,combined with density functional theory,the adsorption mechanism was understood.The results showed that the maximum adsorption capacity of BPT-BZ-CMP was achieved at p H of 6.0 and temperature of35℃,with the maximum of 347.8 mg·g^-1.Considering practical and economic factors,the optimal adsorbent concentration was 0.50 g·L^-1.The adsorption kinetics model and adsorption isotherm of BPT-BZ-CMP followed the pseudo-second-order kinetic model and Liu model,respectively.The adsorption process was a spontaneous and exothermic process,and hydrogen bonding,π-πinteraction and C-H···πinteraction enhanced the adsorption of famciclovir to BPT-BZ-CMP.After four consecutive adsorption-desorption cycles,the adsorption capacity of BPT-BZ-CMP for famciclovir could still reach 91.6%of the initial maximum adsorption capacity.This study provides an excellent solid adsorbent for the efficient removal of famciclovir from water,and demonstrates the application potentiality of CMPs in the field of adsorption.（2）CMP-SO₃Na,a conjugated microporous polymer material,was synthesized through Sonogashira coupling reaction catalyzed by Pd/Cu and used as an adsorbent to remove sulfonamide antibiotics from water,including sulfamethoxazole,sulfamethazine,and sulfadimethoxine.The morphology and characteristics of CMP-SO₃Na were extensively studied using various techniques,such as FT-IR,TG,SEM,and BET.To investigate the adsorption behavior,the effects of solution p H,adsorbent concentration,ionic strength,humic acid,and temperature were analyzed.It was found that CMP-SO₃Na showed good adsorption performance over a wide p H range（2.0-8.0）,with the optimal p H being 6.0.CMP-SO₃Na dosage of 0.50 g·L^-1was determined to be the most economical.The effect of ionic strength and humic acid on the adsorption performance of CMP-SO₃Na was minimal,indicating that CMP-SO₃Na can perform well under different environmental conditions.Under optimal conditions,CMP-SO₃Na material can achieve a maximum adsorption capacity of 219 mg·g^-1,215 mg·g^-1,and238 mg·g^-1for sulfamethoxazole,sulfamethazine,and sulfadimethoxine,respectively.The kinetic curves and adsorption isotherms followed the pseudo-second-order kinetic model and Langmuir model,respectively and the adsorption process was a spontaneous exothermic process.According to density functional theory,hydrogen bonding,π-πinteractions,C-H···πinteractions,and cation-πinteractions played a promoting role in this process.After four adsorption-desorption cycles,the adsorption capacity of CMP-SO₃Na for sulfamethoxazole can still reach 98.36%of the initial maximum adsorption capacity,demonstrating excellent regenerability.This study provides a fast and effective method for removing sulfamethoxazole,sulfamethazine,and sulfadimethoxine from water,demonstrating the excellent performance of conjugated microporous polymer materials in the field of adsorption.