Self-inhibited Multivalent Ion Transport of the Porphyrin-functionalized Amorphous Covalent-Organic Framework Membrane for Efficient Lithium Extraction from Battery Cathodes

doi:10.1007/s40242-026-6075-3

Chemical Research in Chinese Universities ›› 2026, Vol. 42 ›› Issue (5): 1470-1477.doi: 10.1007/s40242-026-6075-3

• Research Articles • Previous Articles Next Articles

Self-inhibited Multivalent Ion Transport of the Porphyrin-functionalized Amorphous Covalent-Organic Framework Membrane for Efficient Lithium Extraction from Battery Cathodes

GONG Yanfeng^1,2, HOU Yushuang^1,2, WANG Tianwen^1,2, WANG Yujue^1,2, XU Yongyuan¹, SUI Kunyan¹, GAO Jun^2,3, LIU Xueli¹

1. College of Materials Science and Engineering, Key Laboratory of Marine Bio-based Fibers of Shandong Province, Key Laboratory of Shandong Provincial Universities for Advanced Fibers and Composites, Qingdao University, Qingdao 266071, P. R. China;
2. Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, P. R. China;
3. Shandong Energy Institute, Qingdao 266101, P. R. China

Received:2026-03-24 Accepted:2026-04-28 Online:2026-10-01 Published:2026-09-24
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 22572099, 22272194), the National Key R&D Program of China (No. 2022YFB3805900), and the Shandong Provincial Natural Science Foundation, China (No. ZR2023MB037).

Abstract

Abstract: The recycling of lithium from spent batteries is crucial for mitigating resource shortages, yet achieving high Li⁺ selectivity over competing multivalent ions remains a major challenge. Here, we report a porphyrin-functionalized amorphous covalent-organic framework (COF) membrane that enables highly selective and efficient Li⁺ separation via self-inhibited multivalent ion transport. The membrane features sub-0.3 nm pores that sterically hinder hydrated multivalent ions, while porphyrin moieties strongly bind multivalent ions, increasing positive surface charge and electrostatically repelling subsequent multivalent ions. This self-inhibition mechanism, combined with distinct weakly interacting pathways for Li⁺, amplifies the Li⁺ selectivity by an order of magnitude, reaching 650 or even higher, depending on the multivalent ion type. Applied to cathode leachates, the membrane achieves Li⁺ purity up to 98.75% for LiFePO₄ and 99.97% for nickel manganese cobalt (NMC) systems via only a single-step separation. This work should guide the development of selective ion recovery methods, highlighting the potential of decoupled ion transport pathways in membrane design.

Key words: Ion sieving, Lithium recycling, Covalent-organic framework (COF), Metal coordination, Membrane separation

GONG Yanfeng, HOU Yushuang, WANG Tianwen, WANG Yujue, XU Yongyuan, SUI Kunyan, GAO Jun, LIU Xueli. Self-inhibited Multivalent Ion Transport of the Porphyrin-functionalized Amorphous Covalent-Organic Framework Membrane for Efficient Lithium Extraction from Battery Cathodes[J]. Chemical Research in Chinese Universities, 2026, 42(5): 1470-1477.

References

[1] Li H., Berbille A., Zhao X., Wang Z., Tang W., Wang Z., Nat. Energy, 2023, 8, 1137.
[2] Tran Mai K., Rodrigues M., Kato K., Babu G., Ajayan P., Nat. Energy, 2019, 4, 339.
[3] Xu Y., Du Y., Chen H., Chen J., Ding T., Sun D., Chem. Soc. Rev., 2024, 53, 7202.
[4] Li Z., Li C., Liu X., Cao L., Li P., Wei R., Li X., Guo D., Huang K., Lai Z., Energy Environ. Sci., 2021, 14, 3152.
[5] Liu D., Qu X., Zhang B., Zhao J., Xie H., Yin H., ACS Sustainable Chem., 2022, 10, 5739.
[6] Zhang L., Liao Y., Ye M., Cai W., Xiao M., Hu C., Zhong B., Wan F., Guo X., ACS Appl. Mater., 2023, 15, 59475.
[7] Harper G., Sommerville R., Kendrick E., Driscoll L., Slater P., Stolkin R., Nature, 2019, 575, 75.
[8] Bae H., Kim Y., Mater. Adv., 2021, 2, 3234.
[9] Piątek J., Afyon S., Tetyana M., Budnyak S., Mika H., Adv. Funct. Mater., 2020, 11, 2003456.
[10] Liu C., Lin J., Cao H., Zhang Y., Sun Z., Cleaner Prod., 2019, 228, 801.
[11] Dai Z., Jin P., Yuan S., Yang J., Agrawal K., Wang H., Nat. Commun., 2025, 16, 4626.
[12] Lee W., Li H., Du Z., Feng D., Chem. Soc. Rev., 2024, 53, 8182.
[13] Lei D., Zhu Y., Lou L., Liu Z., Mater. Horiz., 2025, 12, 5459.
[14] Manzoor S., Younis M., Yao Y., Tariq Q., Zhang B., Tian B., Yan L., Qiu C., Coord. Chem. Rev., 2025, 541, 216840.
[15] Chen S., Zhu C., Xian W., Liu X., Liu X., Zhang Q., Ma S., Sun Q., J. Am. Chem. Soc., 2021, 143, 9415.
[16] Wu T., Qian Y., Zhu Z., Yu W., Zhang L., Liu J., Shen X., Zhou X., Qian T., Yan, C., Adv. Mater., 2025, 37, 2415509.
[17] Su Y., Peng H., Liu X., Li J., Zhao Q., Nat. Commun., 2024, 15, 10295.
[18] Kim T., Kim H., Kim C., Hwang J., Desalination, 2024, 592, 118089.
[19] Xia J., Pan S., Li Q., Fu Q., Song S., Bao S., Sui K., Jiang L., Gao J., Liu X., Water Res., 2025, 285, 124155.
[20] Wang J., Zhang Z., Zhu J., Tian M., Zheng S., Wang F., Wang X., Wang L., Nat. Commun., 2020, 11, 3540.
[21] Xu R., Yu H., Ren J., Zhang W., Kang Y., Wang Z., Feng F., Xia X., Jefferson Z., Peng L., Zhang X., Pan B., J. Am. Chem. Soc., 2025, 147, 17144.
[22] Huang T., Kan X., Fan J., Gao H., Yu L., Zhang L., Xia J., Gao J., Liu X., Sui K., Jiang L., ACS Nano, 2023, 17, 17245.
[23] Zhang Y., Zhou K., Su S., Gao J., Liu J., Jiang L., Sci. Adv., 2024, 10, eadm9620.
[24] Zhang M., Guan K., Ji Y., Liu G., Jin W., Xu N., Nat. Commun., 2019, 10, 1253.
[25] Bao S., Ma Z., Yu L., Li Q., Xia J., Song S., Sui K., Zhao Y., Liu X., Gao J., Nat. Commun., 2025, 16, 3896.
[26] Liu W., Lv C., Hou Y., Ma Z., He M., Sci. China Chem., 2025, 68, 5065.
[27] Hou Y., Zhu C., Sun H., Zhao Y., Pan S., Ma S., Fu Q., Sui X., Liu X., Jiang L., Gao J., Angew. Chem. Int. Ed., 2025, 64, e202504259.
[28] Ding R, Zhu Y., Jing L, Chen S., Lu J., Int. J. Biol. Macromol., 2024, 282, 137037
[29] Sheng L., Zhou Z., Chen A., J. Salt Lake Res., 2025, 33, 87.

Self-inhibited Multivalent Ion Transport of the Porphyrin-functionalized Amorphous Covalent-Organic Framework Membrane for Efficient Lithium Extraction from Battery Cathodes

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 3

Recommended Articles

Metrics

Comments

[1]	JI Changxing, LIN Yangyang, LANG Chao. Self-assembled Isoporous Membranes: From Ordered Block Copolymer Nanopores to Integrated Transport Channels [J]. Chemical Research in Chinese Universities, 2026, 42(5): 1394-1407.
[2]	MA Xinyi, FU Yuan, LIU Jia. Lithium and Scattered Metals from Liquid Ores: A Roadmap for Future Extraction Technologies [J]. Chemical Research in Chinese Universities, 2025, 41(6): 1294-1313.
[3]	MA Hanze, WANG Shaoyu, REN Yanxiong, WANG Yuhan, ZHU Ziting, HE Guangwei, JIANG Zhongyi. Microstructure Manipulation of Covalent Organic Frameworks (COFs)-based Membrane for Efficient Separations [J]. Chemical Research in Chinese Universities, 2022, 38(2): 325-338.