海藻酸钠凝胶微球声光催化降解 17β-雌二醇性能研究

Study on Sonophotocatalytic Degradation of 17β-Estradiol by Sodium Alginate Hydrogel Beads

摘要

针对污水中雌激素去除效率低，且粉末催化剂存在难回收、易团聚等问题，本研究开展固定化海藻酸钠凝胶微球制备及声光催化降解17β-E2 的研究。通过两步水热法合成Er³⁺-CdS/MoS₂（ECMS），负载于海藻酸钠（SA）制备了ECMS-SA凝胶微球催化剂，采用SEM、XRD、FTIR对其形貌、晶相及官能团进行表征，考察其在腐植酸（HA）强化下对水中17β-雌二醇（17β-E2）的声光催化降解性能。结果表明，投加量为2.0 g/L时，反应90 min后凝胶微球催化剂对17β-E2的降解率可达99.33%。五次循环后17β-E2去除率仍维持在92%以上，循环稳定性良好。凝胶微球对模拟污废水中17β-E2、雌酮（E1）和雌三醇（E3）声光催化降解效果良好，其中17β-E2的降解受水质干扰较小，E1和E3的去除则受到共存有机物和离子竞争的影响。该研究旨在为水中雌激素的高效去除提供性能稳定的可回收催化剂与工艺参考。

Abstract

To address the problems of low removal efficiency of estrogens from wastewater and the drawbacks of powder catalysts such as difficult recovery and easy agglomeration, this study focuses on the preparation of immobilized sodium alginate hydrogel beads and their sonophotocatalytic degradation of 17β -E2. Er³⁺-CdS/MoS₂ (ECMS) is synthesized via a two-step hydrothermal method and subsequently immobilized into sodium alginate (SA) to fabricate ECMS-SA hydrogel bead catalysts. The morphology, crystal phase and functional groups of the as-prepared catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). The sonophotocatalytic degradation performance for 17β-estradiol (17β-E2) in aqueous solution in the presence of humic acid (HA) is also investigated. Experimental results show that the degradation efficiency of 17β -E2 reaches 99.33% after 90 minutes of reaction at 2.0 g/L dosage. After five cycles, the removal efficiency of 17β-E2 still remains above 92%, demonstrating good cycling stability. The hydrogel bead exhibits effective sonophotocatalytic degradation performance for 17β-E2, estrone (E1), and estriol (E3) in the simulated wastewater. Among them, the degradation of 17β-E2 is less affected by interference from the water matrix, while the removal of E1 and E3 is influenced by the competitive effects of coexisting organic matter and ions. This study aims to provide a stable and recyclable catalyst and process reference for the efficient elimination of estrogens from aquatic environments.

关键词

声光催化 / 17β-雌二醇 / 凝胶微球 / 循环稳定性 / 模拟污废水

Key words

Sonophotocatalysis / 17β-estradiol / hydrogel bead / cycling stability / simulated wastewater

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基金资助

福建省自然科学基金(2023J02006)

国家自然科学基金(42507114)

山东省自然科学基金(ZR2025QC383)