三维层级花状活性氧化铝纳米材料的制备及其除砷性能研究

doi:10.15541/jim20180317

摘要/Abstract

摘要：

以硝酸铝和尿素为原料, 通过简单的水热和高温煅烧法自组装形成三维层级花状活性氧化铝。这种结构既保留了氧化铝丰富的纳米级别活性位点, 同时具有微米级的三维尺寸, 在柱吸附除砷实验中起到骨架支撑作用, 而其较大的比表面积可以确保水中的砷酸根离子与吸附位点充分接触, 从而有效吸附水中砷酸根离子, 相较商用活性氧化铝具有更好的除砷性能, 且不会对水体产生二次污染。对制备的活性氧化铝材料的除砷动力学进行了分析, 明确了吸附动力学准一级和准二级模型的应用条件和范围。通过对该材料吸附砷酸根前后Zeta电位的变化的研究和离子强度实验进一步验证发现, γ-Al₂O₃对As(V)的吸附机理遵循内球配位模型, 而对As(III)的吸附机理遵循外球配位模型。

关键词: 三维层级花状氧化铝, 晶体生长, 吸附动力学, 吸附模型机理

Abstract:

A 3D flower-like active alumina material was synthesized through a simple hydrothermal method following by calcination at 500 ℃. This structure retains abundant nanoscale active sites and micro-scale 3D size. In the column adsorption test, when the arsenic-contaminated water flows through the material, this 3D hierarchical structure not only serves as a skeleton support, but also provides adsorption site with larger specific surface area so that the arsenate ion can be fully adsorbed. The synthesized alumina in this study performs better arsenic removal than the commercial one without secondary pollution in the water body. The arsenic removal kinetic tests clarify the application conditions of the pseudo first- and second-order adsorption kinetic models. Zeta potential and ionic strength reveal that the mechanism of adsorption of As (V) on γ-Al₂O₃ follows the inner spherical model, while the adsorption of As (III) follows the outer spherical model.

Key words: 3D hierarchical Al₂O₃, crystal growth, adsorption kinetics, adsorption mechanism

中图分类号:

TQ174

李荣辉, 郏义征, 胡楠楠. 三维层级花状活性氧化铝纳米材料的制备及其除砷性能研究[J]. 无机材料学报, 2019, 34(5): 553-559.

Rong-Hui LI, Yi-Zheng JIA, Nan-Nan HU. 3D Hierarchical Flower Like Alumina Nanomaterials: Preparation and Arsenic Removal Performance[J]. Journal of Inorganic Materials, 2019, 34(5): 553-559.

图/表 10

图1 柱吸附除砷实验装置示意图

Fig. 1 Schematic diagram of the column test device for arsenic removal

图2 样品A (a)和样品B (b)的XRD图谱

Fig. 2 XRD patterns of sample A (a) and sample B (b)

图3 不同水热时间的样品经煅烧后得到的样品B(γ-Al2O3)的SEM照片

Fig. 3 SEM images of sample B (γ-Al2O3) calcined from the sample hydrothermal treated for 5 h (a, c) and 12 h (b, d) with the magnification (c,d) of (a) and (b), respectively

图4 花状氧化铝的形成过程示意图

Fig. 4 Scheme for the formation of flower-like alumina

图5 (a)氮气吸附-脱附曲线和H3迟滞回线示意图(插图), (b)孔径分布图

Fig. 5 (a) N2 adsorption desoption curve and schematic diagram of H3 hysteresis loop (inset), and (b) pore size distribution curve

图6 吸附动力学准一次和准二次模型拟合相关系数(R2)与吸附剂用量的关系

Fig. 6 Correlation coefficient (R2) of pseudo 1st and 2nd kinetics models on As(V) with different dosages of adsorbent

图7 (a)制备的氧化铝和(b)商用活性氧化铝的除砷柱吸附实验

Fig. 7 Column test of arsenic removal for (a) as-synthesized Al2O3 and (b) commercial activated Al2O3

图8 竞争离子对γ-Al2O3吸附As(III)和As(V)性能的影响

Fig. 8 Effects of competing ions on the adsorption of As(III) and As(V) onto γ-Al2O3

图9 γ-Al2O3吸附不同浓度As(III) (a)和As(V) (b)后Zeta电位变化

Fig. 9 Zeta potential changes after As(III) (a) and As(V) (b) adsorption

图10 不同pH条件下, 离子强度对As(III) (a)和As(V) (b)吸附量的影响

Fig. 10 Effects of ionic strength on the As(III) (a) and As(V) (b) adsorption capacity at different pH

参考文献 12

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