丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子

doi:10.1016/j.actphy.2025.100066

物理化学学报 >> 2025, Vol. 41 >> Issue (7): 100066.doi: 10.1016/j.actphy.2025.100066

所属专题：电化学分离与资源化

丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子

黄鋆¹, 聂鹏飞¹, 鲁勇朝², 李佳洋³, 王怡文¹, 刘建允¹^,²^,*()

¹ 东华大学环境科学与工程学院, 国家环境保护部纺织污染防治工程技术中心, 上海 201620
² 喀什大学土木工程学院, 新疆喀什 844000
³ 北京化工大学材料科学与工程学院, 北京 100029

收稿日期:2024-12-18 修回日期:2025-01-25 录用日期:2025-02-12 发布日期:2025-05-22
通讯作者: Email: jianyun.liu@dhu.edu.cn (刘建允)
基金资助:
国家自然科学基金(21776045); 上海市自然科学基金(23ZR1401200)

Efficient adsorption of hardness ions by a mordenite-loaded, nitrogen-doped porous carbon nanofiber cathode in capacitive deionization

Jun Huang¹, Pengfei Nie¹, Yongchao Lu², Jiayang Li³, Yiwen Wang¹, Jianyun Liu¹^,²^,*()

¹ College of Environmental Science and Engineering, Textile Pollution Controlling Engineering Center of Ministry of Environmental Protection, Donghua University, Shanghai 201620, China
² School of Civil Engineering, Kashi University, Kashi 844000, Xinjiang Uygur Autonomous Region, China
³ College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

Received:2024-12-18 Revised:2025-01-25 Accepted:2025-02-12 Published:2025-05-22
Contact: Email: jianyun.liu@dhu.edu.cn (Jianyun Liu)
Supported by:
the National Natural Science Foundation of China(21776045); the Natural Science Foundation of Shanghai(23ZR1401200)

1. 2025.100066-SI-3p.pdf(377KB)

摘要/Abstract

摘要：

电容去离子(CDI)是一种具有广阔前景的电脱盐技术。通过引入成本低、无毒的电极材料，CDI在水体硬度离子的选择性去除方面呈现显著优势。丝光沸石(MOR)是天然的、环保型离子交换材料。本研究通过静电纺丝法，将MOR有效嵌入纳米纤维，随后进行炭化处理得到丝光沸石负载氮掺杂碳纳米纤维(MOR@N-CNF)。研究证实了MOR在碳纳米纤维基体中均匀分布。MOR@N-CNF表现出增强的亲水性的高的比表面积。而且纤维柔性好、导电性高，作为自支撑电极在CaCl₂溶液中，呈现高的电化学比电容(162.7 F∙g⁻¹)。直接用于CDI阴极与活性炭(AC)阳极构成非对称CDI系统，进行选择性硬度离子吸附。MOR@N-CNF阴极对Mg²⁺和Ca²⁺的吸附容量分别为1501和1416 μmol∙g⁻¹，且对这两种离子的选择性远高于Na⁺ (对Ca²⁺的选择性系数为9.7，对Mg²⁺的选择性系数为8.9)。经过40次循环测试后，该电极保留了78%的吸附能力，展现出优异的循环稳定性。本研究不仅为离子交换型复合电极材料的制备提供了新思路，也进一步凸显了CDI技术在硬水软化领域的潜力。

关键词: 自支撑, 碳纤维, 电容去离子, 选择性吸附, 硬度离子

Abstract:

Water hardness, predominantly due to the presence of Ca²⁺ and Mg²⁺ ions, presents significant challenges to water quality and public health. Addressing this issue necessitates effective water softening, which remains a pivotal task in water treatment. Capacitive deionization (CDI) has emerged as a promising technology for selective hardness removal, leveraging the low-cost, non-toxic and environmentally friendly selective electrode materials. Electrospun nanofibers, characterized by their three-dimensional porous structure, offer good flexibility, high specific surface area and excellent electrical conductivity. Their components can be tailored to meet the specific requirements. In this study, we incorporated mordenite (MOR), noted for its excellent ion-exchange capacity, into self-supporting nitrogen-doped carbon nanofibers (N-CNF) via electrospinning a blend of polyacrylonitrile (PAN), urea, and MOR, followed by carbonization. The resulting mordenite-loaded N-CNF composite (MOR@N-CNF) exhibited good flexibility and high conductivity. Scanning electron microscopy and X-ray diffraction analysis confirmed the presence and uniform distribution of MOR within the CNF matrix. X-ray photo spectroscopy demonstrated an increase in nitrogen content in MOR@N-CNF. In addition, the MOR@N-CNF composite displayed enhanced hydrophilicity and an increased specific surface area. When used as a self-supporting electrode, MOR@N-CNF exhibited the electrochemical specific capacitance of 162.7 F∙g⁻¹, with the specific capacitance retention of 60% in a CaCl₂ solution. In an asymmetric CDI setup with activated carbon (AC) as the anode, the MOR@N-CNF cathode demonstrated outstanding adsorption capacities of 1501 and 1416 μmol∙g⁻¹ for Mg²⁺ and Ca²⁺, respectively. The composite electrode exhibited high selectivity for Mg²⁺ and Ca²⁺ over Na⁺ with a selectivity factor of 9.7 and 8.9, respectively. These attributes endow the material with exceptional ability to discriminate between divalent and monovalent ions, thereby enhancing its potential for hardness removal. Furthermore, the electrode retained 78% of its adsorption capacity after 40 cycles, demonstrating robust cyclic stability, and ensuring long-term CDI operation. This work provides a new strategy for preparing ion-exchange material-based composite electrodes and highlights the potential of CDI technology in hard water softening.

Key words: Self-supporting, Carbon nanofiber, Capacitive deionization, Selective adsorption, Hardness ion

黄鋆, 聂鹏飞, 鲁勇朝, 李佳洋, 王怡文, 刘建允. 丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子[J]. 物理化学学报, 2025, 41(7), 100066. doi: 10.1016/j.actphy.2025.100066

Jun Huang, Pengfei Nie, Yongchao Lu, Jiayang Li, Yiwen Wang, Jianyun Liu. Efficient adsorption of hardness ions by a mordenite-loaded, nitrogen-doped porous carbon nanofiber cathode in capacitive deionization[J]. Acta Phys. -Chim. Sin. 2025, 41(7), 100066. doi: 10.1016/j.actphy.2025.100066

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100066

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I7/100066

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System	Salt solution	Operation mode	Cell voltage (V)	Γ (μmol∙g⁻¹)	v_D (μmol∙g⁻¹∙min⁻¹)	Ref.
AC\|\|AC	32 mmol∙L⁻¹ MgCl₂	CV	1.0	155	2.6	[37]
Ca-AC\|\|AC(+)	10 mmol∙L⁻¹ CaCl₂	CV	1.2	252	25.2	[38]
Ca-CNT\|\|CNT(+)	18.75 mmol∙L⁻¹ CaCl₂	CV	1.2	386	3.2	[20]
MOR-AC\|\|AC(+)	10 mmol∙L⁻¹ CaCl₂	CC	1.2	248	8.3	[22]
EC-δ-MnO₂\|\|AC(+)	2.5 mmol∙L⁻¹ CaCl₂	CC	−0.75–1.2	350	–	[39]
CuHCF\|\|AC(+)	2.5 mmol∙L⁻¹ CaCl₂	CV	1.2	580	9.7	[40]
MnFe₂O₄\|\|AC(+)	1.5 mmol∙L⁻¹ MgCl₂	CV	1.2	980	8.2	[41]
MnFe₂O₄\|\|AC(+)	1.5 mmol∙L⁻¹ CaCl₂	CV	1.2	534	4.5	[41]
MOR@N-CNF\|\|AC(+)	10 mmol∙L⁻¹ MgCl₂	CC	1.2	1501	50	This work
MOR@N-CNF\|\|AC(+)	10 mmol∙L⁻¹ CaCl₂	CC	1.2	1416	47.2	This work

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丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子

Efficient adsorption of hardness ions by a mordenite-loaded, nitrogen-doped porous carbon nanofiber cathode in capacitive deionization

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