磁性活性炭吸附水中双氯芬酸钠的效能与机制

Adsorption efficiency and mechanism of diclofenac sodium in water using magnetic activated carbon

  • 摘要: 为有效去除水中难生物降解的双氯芬酸钠(DS),并解决吸附剂固液分离难和再生难的难题,本文以Mn0.6Zn0.4Fe2O4(MZF)磁性纳米颗粒为磁核,利用多巴胺(DA)和粉末活性炭(PAC),采用分步沉积法制备得到具有“核-壳”结构的磁性活性炭Mn0.6Zn0.4Fe2O4@PDA-PAC(MZF@PDA-PAC),利用扫描电镜(SEM)、透射电镜(TEM)、磁滞回线(VSM)等对其织构性能、形貌和磁性能等进行了表征,研究了MZF@PDA-PAC对水中DS的吸附等温线、吸附动力学和吸附热力学,利用红外光谱(FTIR)和X射线光电子能谱(XPS)分析了吸附机制。结果表明:MZF@PDA-PAC呈不规则球形,比表面积为752.7 m2∙g−1,具有介孔结构,在水中易分散且具有优异的磁分离性能;MZF@PDA-PAC对水中DS的最大平衡吸附量为114.17 mg·g−1,负载DS的MZF@PDA-PAC可采用0.15 g∙L−1的过硫酸氢钾溶液为再生剂进行原位氧化再生,经过6次吸附-原位氧化再生循环后,MZF@PDA-PAC对DS的平衡吸附量仍保持在75.6 mg·g−1。该吸附过程可用Langmuir等温线和拟二级动力学模型描述,吸附为自发进行的放热过程且伴随体系混乱度降低;MZF@PDA-PAC吸附水中DS以物理吸附为主,吸附速率由表面吸附、颗粒内扩散和化学吸附共同控制,吸附作用力可能有π-π共轭作用、分子间氢键和静电作用等。MZF@PDA-PA具有高稳定性、高容量、能原位氧化再生等优点,在难降解有机污染物去除方面具有广阔的应用前景。

     

    Abstract: To effectively remove non-biodegradable diclofenac sodium (DS) from water and address the challenges of difficult solid-liquid separation and regeneration of adsorbents, this study employed Mn0.6Zn0.4Fe2O4 (MZF) magnetic nanoparticles as the magnetic core, and dopamine (DA) and powdered activated carbon (PAC) were utilized to synthesize the core-shell structured magnetic activated carbon Mn0.6Zn0.4Fe2O4@PDA-PAC (MZF@PDA-PAC) through a step-by-step deposition method. The texture properties, morphology, and magnetic properties of MZF@PDA-PAC were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), hysteresis loop measurements, and other techniques. The adsorption isotherm, kinetics, and thermodynamics of DS adsorption by MZF@PDA-PAC in water were investigated. The mechanism of DS adsorption by MZF@PDA-PAC in water was analyzed using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results indicated that MZF@PDA-PAC exhibited an irregular spherical shape, with a specific surface area of 752.7 m2·g−1, a mesoporous structure, excellent dispersibility in water, and outstanding magnetic separation performance. The maximum equilibrium adsorption capacity of DS adsorbed by MZF@PDA-PAC in water was 114.17 mg·g−1. The DS-loaded MZF@PDA-PAC could be regenerated through in-situ oxidation using a 0.15 g∙L−1 potassium peroxymonosulfate solution as the regenerant. After six adsorption and in-situ oxidation regeneration cycles, the equilibrium adsorption capacity of DS adsorbed by MZF@PDA-PAC remained at 75.6 mg·g−1. The DS adsorption by MZF@PDA-PAC could be described by the Langmuir isotherm and the pseudo-second-order kinetic model, and it is a spontaneous, exothermic process accompanied by a decrease in system entropy. The DS adsorption by MZF@PDA-PAC in water was primarily dominated by physical adsorption, with the adsorption rate controlled by surface adsorption, intra-particle diffusion, and chemical adsorption. The adsorption mechanisms might include π-π conjugation, intermolecular hydrogen bonding, and electrostatic interactions. MZF@PDA-PAC exhibited advantages such as high capacity, the ability for in-situ oxidation regeneration, and high stability, demonstrating broad application prospects in the removal of refractory organic pollutants.

     

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