氯化锌改性樱桃核基生物炭对恩诺沙星的吸附效果

    Adsorption of enrofloxacin by cherry stone-based biochar modified with zinc chloride

    • 摘要: 恩诺沙星(enrofloxacin,ENR)是农业生产中广泛使用的一种抗菌药,其药物残留和耐药危害导致了严重的生态风险。因此,降低或消除ENR残留是生态农业的重点研究内容。该研究利用果业废弃物——樱桃核,通过高温氧化法和氯化锌腐蚀造孔技术,将其制备成一种改性生物炭,用于降低和消除水体ENR污染度。通过比表面积分析和电镜扫描比对,与直接氧化制备的生物炭(primitive biochar,PBC)相比,氯化锌改性生物炭(biochar of ZnCl2 modification,Zn-BC)呈大孔径多片层结构,每层分布大量蜂窝状孔隙,其比表面积多达1 148.79 m2/g,对ENR的最大吸附量显著提高。傅里叶变换红外光谱(Fourier transform infrared spectrophotometer, FT-IR)和X射线电子能谱(X-ray photoelectron spectroscopy, XPS)分析表明,Zn-BC具有更多含氧基团,促进其与ENR形成更多配合物,吸附机制可能与孔隙填充、π-π键相互作用、氢键作用有关;吸附动力学和吸附等温模型拟合发现,PBC和Zn-BC均与准二级动力学模型和Langmuir等温吸附模型吻合较好,证实表征分析结果与吸附机理相呼应;热力学分析进一步表明两种生物炭对ENR吸附为自发、熵增加和放热过程。综上,与PBC相比,Zn-BC吸附面积大、效率高,是消除水体ENR残留污染的良好材料。

       

      Abstract: Abstract: Enrofloxacin (ENR) is one type of widely-used potent antibacterial drug to treat the bacterial infections of cultured animals. However, the ingested ENR cannot be fully metabolized or absorbed. About 15%-50% of the original ENR is discharged into the external environment and wastewater in the form of urine, resulting in serious antibiotic pollution. Furthermore, the low removal performance of traditional sewage treatment plants has led to the widespread antibiotic residues in surface water, underground water, and even drinking water. And drug contamination caused by these residues and the development of drug-resistance genes can pose serious ecological risks. Biochar (a new type of carbon material adsorbent) can be expected to serve as antibiotic removal, due to the extremely low entry conditions, extensive and cost-free raw materials, and renewable properties. Tianshui City of Gansu Province is one of the main cherry-producing areas in China. The resulting cherry stone has been a solid waste. A few cherry stones have been used for pillow primary processing and utilization. But most of them have been discarded, leading to a waste of resources and great pollution to the environment. As a result, there is a high demand for the processing and utilization of cherry stone. Taking the cherry stone (an agricultural solid waste) as the raw material, this study aims to prepare the biochar composites using high-temperature pyrolysis. Zinc chloride was also used to modify the property. N2 adsorption-desorption experiment and scanning electron microscopy (SEM) were used to determine the specific surface area, porosity, and morphology of unmodified biochar (PBC) and modified biochar (Zn-BC). Fourier infrared spectroscopy (FT-IR) and X-ray electron spectroscopy (XPS) were used to characterize the composition of active groups and functional groups before and after the adsorption of ENR by PBC and Zn-BC, respectively. Adsorption kinetics and isothermal adsorption experiments were used to clarify the adsorption mechanism of ENR by the two kinds of carbon. The results show that the surface aperture of PBC was relatively less, and the surface was mostly porous and smooth. Zn-BC exhibited a large pore size and layered structure, where each layer was distributed with a large number of honeycomb pore sizes, and the surface was irregular with the larger specific surface area and more pore structure. The specific surface area was 1 148.79 m2/g, which was 2.5 times that of PBC. The total pore volume increased by nearly 85 times. Zinc chloride changed the structure of biochar by etching holes on the biochar skeleton. The modified biochar shared a better adsorption effect on ENR, indicating a higher adsorption capacity than PBC. IR and XPS analysis confirmed that Zn-BC also introduced more oxygen-containing functional groups. The adsorption was attributed to the formation of complexes between ENR and oxygen-containing functional groups. As such, the adsorption mechanism was related to the pore filling, π-π bond interaction, and hydrogen bond interaction. The adsorption kinetics and adsorption isothermal model fitted better with the quasi-second-order kinetic model and Langmuir isothermal adsorption model. The chemical adsorption of ENR was dominated by the two biochar types. The adsorption was mainly controlled by pore filling, π-π bond interaction and hydrogen bond, indicating the single-layer adsorption. There was better consistency with the previous analysis of IR and XPS. The particle diffusion model showed that the ENR was firstly adsorbed by the outer surface of Zn-BC during the whole adsorption. And then ENR was adsorbed by the inner surface in the Zn-BC micropore. This adsorption was controlled by intra-particle diffusion. Thermodynamic analysis showed that gibbs free energy (G0) and enthalpy change (H0) of both biochars were negative, but entropy change (S0) of both biochars was positive, indicating the spontaneous adsorption ENR by both biochars, increasing entropy and exothermic reaction. Therefore, Zn-BC-modified biochar can be used as a better material to remove ENR in water, particularly for the water treatment and remediation caused by antibiotic pollution.

       

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