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

Abstract

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

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

Figures/Tables 10

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References 45

1	Ayaz, M.; Namazi, M. A.; Din, M. A. U.; Ershath, M. I. M.; Mansour, A.; Aggoune, E.-H. M. Desalination 2022, 540, 116022. doi: 10.1016/j.desal.2022.116022
2	Egbueri, J. C. Environ. Sci. Pollut. Res. Int. 2023, 30(22), 61626. doi: 10.1007/s11356-023-26396-5
3	Gitis, V.; Hankins, N. J. Water Process Eng. 2018, 25, 34. doi: 10.1016/j.jwpe.2018.06.003
4	Wu, Q.; Liang, D.; Lu, S.; Wang, H.; Xiang, Y.; Aurbach, D.; Avraham, E.; Cohen, I. Desalination 2022, 542, 116043. doi: 10.1016/j.desal.2022.116043
5	Alaei Shahmirzadi, M. A.; Hosseini, S. S.; Luo, J.; Ortiz, I. J. Environ. Manage. 2018, 215, 324. doi: 10.1016/j.jenvman.2018.03.040
6	Dou, W.; Zhou, Z.; Jiang, L. M.; Jiang, A.; Huang, R.; Tian, X.; Zhang, W.; Chen, D. J. Environ. Manage. 2017, 196, 518. doi: 10.1016/j.jenvman.2017.03.054
7	Afsari, M.; Shon, H. K.; Tijing, L. D. Adv. Colloid Interface Sci. 2021, 289, 102362. doi: 10.1016/j.cis.2021.102362
8	Xiong, Y.; Yu, F.; Ma, J.. Acta Phys. Chim. Sin. 2022, 38(5), 2006037. doi: 10.3866/PKU.WHXB202006037
	熊岳城, 于飞, 马杰. 物理化学学报, 2022, 38(5), 2006037. doi: 10.3866/PKU.WHXB202006037
9	Wang, L.; Yu, F.; Ma, J.. Acta Phys. Chim. Sin. 2017, 33(7), 1338. doi: 10.3866/PKU.WHXB201704113
	王雷, 于飞, 马杰. 物理化学学报, 2017, 33(7), 1338. doi: 10.3866/PKU.WHXB201704113
10	Sivasubramanian, P.; Kumar, M.; Kirankumar, V. S.; Samuel, M. S.; Dong, C.-D.; Chang, J.-H. Desalination 2023, 559, 116652. doi: 10.1016/j.desal.2023.116652
11	Zhao, X.; He, Z.; Li, M.; He, C.; Xu, Y.; Wang, Y.; Ma, J.; Yang, H. Y. Desalination 2025, 597, 118377. doi: 10.1016/j.desal.2024.118377
12	Porada, S.; Zhao, R.; van der Wal, A.; Presser, V.; Biesheuvel, P. M. Prog. Mater Sci. 2013, 58(8), 1388. doi: 10.1016/j.pmatsci.2013.03.005
13	Tang, W.; Liang, J.; He, D.; Gong, J.; Tang, L.; Liu, Z.; Wang, D.; Zeng, G. Water Res. 2019, 150, 225. doi: 10.1016/j.watres.2018.11.064
14	Lu, M.; Liu, J. Y.; Cheng, J.; Wang, S. P.; Yang, J. M.. Acta Phys. Chim. Sin 2014, 30(12), 2263. doi: 10.3866/PKU.WHXB201410141
	卢淼, 刘建允, 程健, 王世平, 杨健茂. 物理化学学报, 2014, 30(12), 2263. doi: 10.3866/PKU.WHXB201410141
15	Wang, D.; Zhang, Y.; Dong, H.; Chen, H.; SenGupta, A. Environ. Sci. Water Res. Technol. 2024, 10(6), 1319. doi: 10.1039/d4ew00125g
16	Sharma, V.; Mishra, S.; raj, S. K.; Upadhyay, P.; Kulshrestha, V. Colloids Surf. A 2023, 676, 132064. doi: 10.1016/j.colsurfa.2023.132064
17	Li, J.; Corma, A.; Yu, J. Chem. Soc. Rev. 2015, 44(20), 7112. doi: 10.1039/c5cs00023h
18	Gao, S.; Wang, S.; Sun, Y.; Wang, J.; Hu, P.; Shang, J.; Ma, Z.; Liang, Y. Renewable Energy 2023, 215, 119033. doi: 10.1016/j.renene.2023.119033
19	Nakamoto, K.; Ohshiro, M.; Kobayashi, T. J. Environ. Chem. Eng. 2017, 5(1), 513. doi: 10.1016/j.jece.2016.12.031
20	Liu, Y.; Ma, W.; Cheng, Z.; Xu, J.; Wang, R.; Gang, X. Desalination 2013, 326, 109. doi: 10.1016/j.desal.2013.07.022
21	Kim, C.; Lee, J.; Kim, S.; Yoon, J. Desalin. Water Treat. 2016, 57(51), 24682. doi: 10.1080/19443994.2016.1152638
22	Nie, P.; Hu, B.; Shang, X.; Xie, Z.; Huang, M.; Liu, J. Sep. Purif. Technol. 2020, 250, 117240. doi: 10.1016/j.seppur.2020.117240
23	Liu, J.; Wang, S.; Yang, J.; Liao, J.; Lu, M.; Pan, H.; An, L. Desalination 2014, 344, 446. doi: 10.1016/j.desal.2014.04.015
24	Pan, H.; Yang, J.; Wang, S.; Xiong, Z.; Cai, W.; Liu, J. J. Mater. Chem. A 2015, 3(26), 13827. doi: 10.1039/c5ta02954f
25	Wang, R.; Hu, D.; Du, P.; Weng, X.; Tang, H.; Zhang, R.; Song, W.; Lin, S.; Huang, K.; Zhang, R.; et al. Front. Chem. 2021, 9, 812375. doi: 10.3389/fchem.2021.812375
26	Xu, Z.; Ye, J.; Pan, Y.; Liu, K.; Liu, X.; Shui, J. Energy Technol. 2022, 10(4), 2101024. doi: 10.1002/ente.202101024
27	Zhang, H.; Xie, Z.; Wang, Y.; Shang, X.; Nie, P.; Liu, J. RSC Adv. 2017, 7(87), 55224. doi: 10.1039/c7ra12001j
28	Nie, P.; Wang, S.; Shang, X.; Hu, B.; Huang, M.; Yang, J.; Liu, J. Desalination 2021, 520, 115340. doi: 10.1016/j.desal.2021.115340
29	Luo, M.; Chen, J.; Li, Q.; Wang, Y. Industrial & Engineering Chemistry Research 2023, 62(22), 8744. doi: 10.1021/acs.iecr.3c00807
30	Zhou, Q.; Lv, G.; Li, H.; Hu, S.; Liu, H.; Li, L.; He, L.; Li, H.; Hu, P.; Wang, J. J. Power Sources 2024, 623, 235509. doi: 10.1016/j.jpowsour.2024.235509
31	Lankapati, H. M.; Lathiya, D. R.; Choudhary, L.; Dalai, A. K.; Maheria, K. C. ChemistrySelect 2020, 5(3), 1193. doi: 10.1002/slct.201903715
32	Kalijadis, A.; Gavrilov, N.; Jokić B.; Gilić M.; Krstić A.; Pašti, I.; Babić B. Mater. Chem. Phys. 2020, 239, 122120. doi: 10.1016/j.matchemphys.2019.122120
33	Ajravat, K.; Rajput, S.; Brar, L. K. Diamond Relat. Mater. 2022, 129, 109373. doi: 10.1016/j.diamond.2022.109373
34	Tan, B.; Li, H.; Yuan, Q.; An, F. Mater. Today Commun. 2024, 41, 110459. doi: 10.1016/j.mtcomm.2024.110459
35	Zheng, Y.; Chen, K.; Jiang, K.; Zhang, F.; Zhu, G.; Xu, H. J. Energy Storage. 2022, 56, 105995. doi: 10.1016/j.est.2022.105995
36	Abbas, Q.; Mirzaeian, M.; Ogwu, A. A.; Mazur, M.; Gibson, D. Int. J. Hydrogen Energy 2020, 45(25), 13586. doi: 10.1016/j.ijhydene.2018.04.099
37	Hou, C.-H.; Huang, C.-Y. Desalination 2013, 314, 124. doi: 10.1016/j.desal.2012.12.029
38	Yoon, H.; Lee, J.; Kim, S.-R.; Kang, J.; Kim, S.; Kim, C.; Yoon, J. Desalination 2016, 392, 46. doi: 10.1016/j.desal.2016.03.019
39	Leong, Z. Y.; Zhang, J.; Vafakhah, S.; Ding, M.; Guo, L.; Yang, H. Y. Desalination 2021, 520, 115374. doi: 10.1016/j.desal.2021.115374
40	Xu, Y.; Zhou, H.; Wang, G.; Zhang, Y.; Zhang, H.; Zhao, H. ACS Appl. Mater Interfaces 2020, 12(37), 41437. doi: 10.1021/acsami.0c11233
41	Xu, Y.; Xiang, S.; Zhou, H.; Wang, G.; Zhang, H.; Zhao, H. ACS Appl. Mater Interfaces 2021, 13(32), 38886. doi: 10.1021/acsami.1c09996
42	Gao, F.; Du, X.; Hao, X.; Ma, X.; Chang, L.; Han, N.; Guan, G.; Tang, K. Chem. Eng. J. 2020, 380, 122413. doi: 10.1016/j.cej.2019.122413
43	Niu, Y.; Meng, K.; Ming, S.; Chen, H.; Yu, X.; Rong, J.; Li, X. Diamond Relat. Mater. 2023, 136, 109925. doi: 10.1016/j.diamond.2023.109925
44	Wang, B.; Koike, N.; Iyoki, K.; Chaikittisilp, W.; Wang, Y.; Wakihara, T.; Okubo, T. Phys. Chem. Chem. Phys. 2019, 21(7), 4015. doi: 10.1039/c8cp06975a
45	Huyskens, C.; Helsen, J.; de Haan, A. B. Desalination 2013, 328, 8. doi: 10.1016/j.desal.2013.07.002

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

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