γ-Al2O3/CuO-ACF电吸附除盐的影响因素及反应动力学

doi:10.16085/j.issn.1000-6613.2023-1600

化工进展 ›› 2024, Vol. 43 ›› Issue (3): 1637-1647.DOI: 10.16085/j.issn.1000-6613.2023-1600

• 资源与环境化工 • 上一篇

γ-Al₂O₃/CuO-ACF电吸附除盐的影响因素及反应动力学

柴多生¹(), 高峰², 吴友兵³, 孙昕¹(), 郝然¹, 杨宇², 焦翔飞¹

^1.西安建筑科技大学环境与市政工程学院，陕西西安 710055
^2.内蒙古自治区水利科学研究院，内蒙古呼和浩特 010011
^3.马鞍山市城乡规划设计院有限责任公司，安徽马鞍山 243011

收稿日期:2023-09-11 修回日期:2023-11-20 出版日期:2024-03-10 发布日期:2024-04-11
通讯作者: 孙昕
作者简介:柴多生（1995—），男，硕士研究生，主要研究方向为微咸水淡化。E-mail：cds1712@126.com。
基金资助:
内蒙古自治区水利科技项目(NSK202002);陕西省自然科学基金重点项目(2023-JC-ZD-28);陕西省重点研发计划(2023GXLH-056)

Reaction dynamics and influencing factors of capacitive deionization desalination using γ-Al₂O₃/ CuO-ACF

CHAI Duosheng¹(), GAO Feng², WU Youbing³, SUN Xin¹(), HAO Ran¹, YANG Yu², JIAO Xiangfei¹

^1.School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055，Shaanxi, China
^2.Inner Mongolia Hydraulic Research Institute, Hohhot 010011, Inner Mongolia, China
^3.Urban & Rural Planning & Design Institute of Ma’anshan, Ma’anshan 243011, Anhui, China

Received:2023-09-11 Revised:2023-11-20 Online:2024-03-10 Published:2024-04-11
Contact: SUN Xin

摘要/Abstract

摘要：

开发脱盐率高、寿命长的电极材料是电容去离子（CDI）水处理技术的研究热点之一。通过一锅水热法将层状CuAl双金属氧化物与活性碳纤维复合，成功制备了CDI电极（γ-Al₂O₃/CuO-ACF）。采用SEM、XRD、FTIR和CV测试对样品的形貌、结构和电极性能进行了表征。当初始NaCl浓度为500mg/L时，随着电压从0.8V逐渐增加到1.6V，两种电极的比吸附量、脱盐效率、电流效率和电耗均有所增加，γ-Al₂O₃/CuO-ACF的四项参数依次比ACF提高23.4%~55.3%、44.8%~82.0%、65.5%~90.0%和降低15.0%~21.4%。当腐殖酸浓度为5~10mg/L时，ACF脱盐效率下降明显，而γ-Al₂O₃/CuO-ACF脱盐效率仅在腐殖酸浓度10mg/L时略有下降。在15次循环后，NaCl溶液体系的脱盐效率保留率为96%；但由于腐殖酸的存在，该值下降为92%。两种电极的电吸附除盐过程遵循Langmuir等温吸附方程，表示盐离子在电极表面为单分子层物理吸附。与传统ACF电极相比，γ-Al₂O₃/CuO-ACF电极具有优异的可回收性、稳定性和增强的电化学特性。

关键词: 层状CuAl双金属氧化物, 活性碳纤维, 脱盐, 电吸附

Abstract:

Developing electrode materials with a high desalination rate and long life is one of the research hotspots in the field of capacitive deionization (CDI) water treatment technology. CDI electrode (γ-Al₂O₃/ CuO-ACF) was successfully produced by combining laminated CuAl-mixed metal oxide with activated carbon fibers with a one-pot hydrothermal method. The surface morphology, structure and electrode properties of the samples were characterized by SEM, XRD, FTIR and CV. When the voltage increased from 0.8V to 1.6V under NaCl concentration of 500mg/L, the specific electroabsorption capacity, desalination efficiency, current efficiency and energy consumption increased for both electrodes, while those four parameters for γ-Al₂O₃/ CuO-ACF were 23.4%—55.3% higher, 44.8%—82.0% higher, 65.5%—90.0% higher and 15.0%—21.4% lower than those for ACF. Under NaCl concentration of 500mg/L and humic acid concentrations of 5—10mg/L, desalination efficiency for ACF was decreased, but that for γ-Al₂O₃/CuO-ACF was only decreased at humic acid concentration of 10 mg/L. After 15 desalination cycles, the retention rate of desalination efficiency was 96% for NaCl solution system, but that was decreased to 92% with the addition of humic acid. The ion adsorption processes for both cases followed the Langmuir isotherm adsorption kinetic equation, indicating that the salt ions were physically adsorbed on the electrode surface as a single molecular layer. Compared with conventional ACF electrodes, the γ-Al₂O₃/CuO-ACF electrode had excellent recoverability, stability and enhanced electrochemical properties.

Key words: laminated CuAl-mixed metal oxide, activated-carbon fiber, desalination, capacitive deionization

中图分类号:

柴多生, 高峰, 吴友兵, 孙昕, 郝然, 杨宇, 焦翔飞. γ-Al₂O₃/CuO-ACF电吸附除盐的影响因素及反应动力学[J]. 化工进展, 2024, 43(3): 1637-1647.

CHAI Duosheng, GAO Feng, WU Youbing, SUN Xin, HAO Ran, YANG Yu, JIAO Xiangfei. Reaction dynamics and influencing factors of capacitive deionization desalination using γ-Al₂O₃/ CuO-ACF[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1637-1647.

图/表 18

图1 电极材料改性过程示意图

图2 CDI实验装置示意图

图3 ACF和γ-Al2O3/CuO-ACF的SEM图

图4 ACF和γ-Al2O3/CuO-ACF的XRD图谱

图5 ACF和γ-Al2O3/CuO-ACF的XRD图谱与FTIR图谱

图6 ACF和γ-Al2O3/CuO-ACF的N2吸附-解吸等温线和孔径分布

图7 ACF和γ-Al2O3/CuO-ACF材料在1mol/L的NaCl电解液中扫描速率为10mV/s时记录的CV曲线

图8 不同材料、不同工作电压下电导率随时间的变化

图9 不同电压下γ-Al2O3/CuO-ACF‖ACF和ACF‖ACF系统的电吸附容量、去除率、能耗和充电效率

图10 500mg/L、1.4V下γ-Al2O3/CuO-ACF‖ACF和ACF‖ACF体系电能吸附实验的再生曲线

表1 不同电极材料除盐能力的比较

电极材料	外加电压 /V	初始浓度 /mg·L^-1	SAC /mg·g^-1	参考文献
ACF-HNO₃	1.2	500	12.80	[38]
NPC@ACF	1.2	500	14.63	[39]
Al₂O₃-ACF	2.0	500	12.25	[17]
ACF	1.4	500	10.16	本工作
γ-Al₂O₃/CuO-ACF	1.4	500	16.97	本工作

图11 不同HA浓度条件下ACF电极和γ-Al2O3/CuO-ACF电极15次脱盐循环实验的去除率

图12 ACF电极反应前后的SEM图

图13 γ-Al2O3/CuO-ACF电极反应前后的SEM图

图14 Langmuir等温吸附线拟合

表2 不同电压下ACF和γ-Al2O3/CuO-ACF电极的Langmuir等温线参数比较

外加电压 /V	ACF				γ-Al₂O₃/CuO-ACF
外加电压 /V	R²	Q_m/mg·g^-1	K_L	R_L	R²	Q_m/mg·g^-1	K_L	R_L
0.8	0.9944	13.26	0.0048	0.8065	0.9988	11.12	0.0089	0.1841
1.0	0.9935	13.81	0.0053	0.7891	0.9960	14.06	0.0102	0.1633
1.2	0.9931	13.94	0.0067	0.7491	0.9966	15.20	0.0148	0.1189
1.4	0.9925	14.48	0.0080	0.7135	0.9912	15.73	0.0292	0.0640
1.6	0.9923	16.25	0.0086	0.6993	0.9946	19.05	0.0410	0.0465

图15 Freundlich等温吸附线拟合

表3 不同电压下ACF和γ-Al2O3/CuO-ACF电极的Freundlich等温线参数比较

外加电压 /V	ACF			γ-Al₂O₃/CuO-ACF
外加电压 /V	R²	K_F	n	R²	K_F	n
0.8	0.9689	0.1485	1.4858	0.9888	0.3918	1.9290
1.0	0.9706	0.1891	1.4570	0.9832	0.5065	1.9488
1.2	0.9765	0.1945	1.4270	0.9855	0.7124	1.9222
1.4	0.9894	0.2504	1.4531	0.9845	1.1903	2.0099
1.6	0.9915	0.2718	1.3894	0.9854	1.4228	1.9410

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γ-Al₂O₃/CuO-ACF电吸附除盐的影响因素及反应动力学

Reaction dynamics and influencing factors of capacitive deionization desalination using γ-Al₂O₃/ CuO-ACF

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