改性纳米纤维素微球的制备及其吸附水中四环素性能研究

Study on the preparation of modified nanocellulose microspheres and their adsorption properties for tetracycline removal from water

摘要

[目的]针对水体中四环素类抗生素污染问题，本研究旨在制备一种能有效去除的纤维素类吸附材料。[方法]以细菌纤维素为原材料，制备改性纳米纤维素微球。首先采用扫描电镜、红外光谱、X射线衍射、热重分析、比表面积和孔径分析等表征方法分析微球的结构特性。然后，研究四环素初始浓度、pH值、吸附时间和温度等对吸附效果的影响，并确定其吸附动力学和吸附等温线。[结果]电镜观察显示，改性纤维素微球大小均匀，直径约300μm。红外光谱证实纳米纤维素经三氨基苯硼酸改性成功。X射线衍射表明改性纳米纤维素的晶型发生改变。热重分析表明改性后制备的纤维素微球的耐热性能加强。改性纳米纤维素微球的比表面积为36.858m²·g^-1，平均孔径13.394nm，孔隙容量0.128cm³·g^-1。改性纳米纤维素微球在四环素质量浓度为300mg·L^-1、吸附温度35℃、pH3时吸附性能最佳。高浓度Ca²⁺、Mg²⁺极显著影响吸附性能(P<0.01)，而Na⁺、K⁺等离子对吸附的影响不显著(P>0.05)。改性纤维素微球对盐酸四环素的吸附量为77.81mg·g^-1，其吸附过程更符合准二级动力学模型，吸附等温曲线更符合Freundlich模型。[结论]改性纳米纤维素微球具有吸附污水中四环素类抗生素的能力，且制备简单，成本低廉，具有较好的应用前景。

Abstract

[Objectives] This study aimed to prepare a cellulose-based absorbent material capable of effectively removing the contamination of tetracycline antibiotics in water bodies. [Methods] The modified nanocellulose microspheres were fabricated using bacterial cellulose as the raw material. Firstly, the structural properties of the microspheres were comprehensively characterized using scanning electron microscopy (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and Brunauer-Emmett-Teller (BET) specific surface area and porosity analysis. Subsequently, the effects of initial tetracycline concentration, pH values, adsorption time, and temperature on adsorption performance were systematically investigated. Furthermore, the adsorption kinetics and isotherms were determined. [Results] SEM images revealed that the modified nanocellulose microspheres were uniform in size, with an average diameter of approximately 300 μm. Fourier transform infrared (FT-IR) spectra confirmed the successful grafting of 3-aminophenylboronic acid onto the nanocellulose surface. XRD pattern indicated an alteration in the crystalline structure of cellulose following modification. TG analysis demonstrated enhanced thermal stability of the modified nanocellulose microspheres. BET analysis determined that the specific surface area, average pore diameter, and pore volume were 36.858 m²·g^-1, 13.394 nm, and 0.128 cm³·g^-1, respectively. Optimal adsorption performance was achieved under the following conditions: tetracycline concentration of 300 mg·L^-1, temperature of 35 ℃, and pH 3. The presence of Na⁺ and K⁺ had a negligible impact on adsorption (P>0.05), whereas high concentrations of Ca²⁺ and Mg²⁺ significantly reduced the adsorption capacity (P<0.01). Under these optimized conditions, the maximum adsorption capacity of the modified cellulose microspheres for tetracycline hydrochloride reached 77.81 mg·g^-1. The adsorption process was better described by the pseudo-second-order kinetic model, and the equilibrium data are better fitted by the Freundlich model. [Conclusions] The synthesized modified nanocellulose microspheres exhibit potential for removing tetracycline antibiotics from wastewater, offering advantages such as straightforward preparation and cost-effectiveness, thus positioning them as a promising candidate for practical application.

关键词

纳米纤维素 / 微球 / 吸附 / 四环素 / 废水处理

Key words

nanocellulose / microspheres / adsorption / tetracycline / wastewater treatment

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基金资助

陕西省重点研发计划项目(S2020-YF-YBNY-0437)