Al2O3/AC正极选择性电容吸附水中氟离子

doi:10.11949/0438-1157.20201305

摘要/Abstract

摘要：

氟是人类生命活动必需的微量元素之一，但人体摄入过多的氟元素会引发氟斑牙、骨骼变形等氟中毒现象。本文以活性炭（AC）为载体，在多孔Al₂O₃纳米分散液中采用简单超声处理，得到Al₂O₃/AC复合材料。场发射扫描电镜证明Al₂O₃成功负载在AC表面，5% Al₂O₃在AC表面分布均匀。N₂吸-脱附测试结果表明Al₂O₃/AC复合材料的比表面积比AC有明显增加。循环伏安、恒流充放电及电化学阻抗测试结果表明Al₂O₃的掺杂可以改善AC的离子导电性，提高比电容；5% Al₂O₃/AC导电性最佳，比电容最高，在7 mmol·L^-1 NaF溶液中为92 F·g^-1，是AC比电容（62 F·g^-1）的1.5倍。以Al₂O₃/AC为正极的电容去离子（CDI）脱氟测试，结果表明5% Al₂O₃/AC电极脱氟量最大，达234 μmol·g^-1，远高于纯AC的脱氟量（115 μmol·g^-1）。此外，5% Al₂O₃/AC电极对F^-的选择性吸附性能良好，在含F^-、Cl^-和SO₄^2-的模拟高氟地下水中采用5% Al₂O₃/AC电极对应的三组CDI池串联，可脱除80%的F^-、25%的Cl^-和56%的SO₄^2-，同时经过十次F^-吸脱附循环后，氟去除率仍可保持81%，证明5% Al₂O₃/AC电极对F^-具有良好的选择吸附性和循环稳定性。该电极材料制备简单，脱氟选择性好，在CDI过程中有望用于高氟地区地下水的净化脱氟。

关键词: 活性炭, Al₂O₃, 电容去离子, 选择性脱氟, 地下水

Abstract:

Fluorine is one of the essential trace elements in human life activities, but excessive intake of fluorine will cause fluorosis such as dental fluorosis and skeletal deformation. In this paper, the Al₂O₃/AC composite material was obtained through simple sonication of activated carbon (AC) and Al₂O₃ nanoparticle. Field emission scanning electron microscopy proved that Al₂O₃ was successfully loaded on the AC surface with a uniform distribution at the doping amount of Al₂O₃ of 5%. The results of N₂adsorption-desorption test showed that the specific surface area of the Al₂O₃/AC composite increased. Cyclic voltammetry, constant current charge discharge and electrochemical impedance measurements demonstrated the improvement of ionic conductivity and specific capacitance of the composite after Al₂O₃ doping. Effect of Al₂O₃ doping amount was investigated and the 5% Al₂O₃/AC electrode achieved the optimal capacity of 92 F·g^-1 in 7 mmol·L^-1 NaF solution, better than that on AC electrode (62 F·g^-1). When being applied as the anode in capacitive deionization device, the Al₂O₃/AC electrode exhibited a defluorination capacity of 234 μmol·g^-1, much higher than that on AC electrode (115 μmol·g^-1). In addition, the 3-cell CDI stack delivered a 80% removal of F^-in the simulated groundwater containing F^-, Cl^- and SO₄^2-, while only 25% of Cl^- and 56% of SO₄^2-were removed. It demonstrated the excellent selective defluorination performance. The adsorption amount of F^- retained 81% after 10 adsorption/desorption cycles. The electrode material is simple to prepare and has good defluorination selectivity. It is expected to be used in the purification and defluorination of groundwater in high-fluorine areas in the CDI process.

Key words: activated carbon, Al₂O₃, capacitive deionization, selective defluorination, groundwater

中图分类号:

O 646

蒋雯雯, 聂鹏飞, 胡彬, 李菁菁, 刘建允. Al₂O₃/AC正极选择性电容吸附水中氟离子[J]. 化工学报, 2021, 72(5): 2817-2825.

JIANG Wenwen, NIE Pengfei, HU Bin, LI Jingjing, LIU Jianyun. Selective capacitive adsorption of fluoride ions with Al₂O₃/AC anode[J]. CIESC Journal, 2021, 72(5): 2817-2825.

图/表 8

图1 AC (a), 3% Al2O3/AC (b), 5% Al2O3/AC (c)和 7% Al2O3/AC (d)的FESEM图

Fig.1 FESEM images of AC (a), 3% Al2O3/AC (b), 5% Al2O3/AC (c) and 7% Al2O3/AC (d)

图2 AC和5% Al2O3/AC电极的N2吸-脱附等温线(a)；孔径分布图(b)

Fig.2 N2 sorption isotherms (a) and pore-size distribution (b) of AC and 5% Al2O3/AC electrodes

表1 样品的孔隙率参数

Table 1 The porosity parameters of various samples

样品

比表面积/

(m²·g^-1)

总孔孔容/

(cm³·g^-1)

微孔孔容/

(cm³·g^-1)

5% Al₂O₃/AC

图3 AC, 3% Al2O3/AC, 5% Al2O3/AC和7% Al2O3/AC电极的CV曲线(a)；电极在不同扫速下对应的比电容值曲线(b); 不同电极的GCD曲线 (c)；不同电极的EIS曲线(d)（电解液：7 mmol·L-1 NaF溶液）

Fig.3 The CV curves of AC, 3% Al2O3/AC, 5% Al2O3/AC and 7% Al2O3/AC electrodes (a); The specific capacitance of electrodes at various scan rates (b); The GCD curves of different electrodes (c); EIS curves of the different electrodes (d)(Electrolyte: 7 mmol·L-1 NaF solution)

图4 3% Al2O3/AC‖AC、5% Al2O3/AC‖AC、7% Al2O3/AC‖AC和 AC‖AC电容器中NaF浓度随时间变化曲线及对应的电压曲线(a)；不同电极的脱氟量(b)

Fig.4 The curves of NaF concentration vs. time and the corresponding voltage vs. time of 3% Al2O3/AC‖AC, 5% Al2O3/AC‖AC, 7% Al2O3/AC‖AC, AC‖AC capacitors (a); Defluorination of different electrodes (b)

图5 在不同NaF浓度下，脱氟量随时间变化的曲线

Fig.5 The curves of defluorination vs. time at different NaF concentration

图6 不同F-/Cl-浓度比对应的选择性系数α值(a)；不同F-/SO42-浓度比对应的选择性系数α值(b)

Fig.6 The selectivity α values corresponding to different F-/Cl- concentration ratio (a); The selectivity α values corresponding to different F-/SO42- concentration ratio (b)

图7 模拟地下水中不同阴离子的去除率(a)；多次循环的脱氟量保持率(b)

Fig.7 Removal rates of different anions in simulated groundwater (a); Retention of F- removal in multiple cycles (b)

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Al₂O₃/AC正极选择性电容吸附水中氟离子

Selective capacitive adsorption of fluoride ions with Al₂O₃/AC anode

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