Coupling Interfacial Redox‐Reactions with In Situ Proton Generation for the Photoelectrochemical Separation of Rare‐Earth Elements

Cho, Ki‐Hyun; Oh, Wangsuk; Fournier, Melanie J.; Su, Xiao

doi:10.1002/adfm.202502529

Title: Coupling Interfacial Redox‐Reactions with In Situ Proton Generation for the Photoelectrochemical Separation of Rare‐Earth Elements

Journal Article · 19 May 2025 · Advanced Functional Materials

DOI: https://doi.org/10.1002/adfm.202502529 · OSTI ID:2567693

Cho, Ki‐Hyun ^[1]; Oh, Wangsuk ^[1]; Fournier, Melanie J. ^[1];

^[1]

Department of Chemical and Biomolecular Engineering University of Illinois at Urbana‐Champaign Urbana IL 61801 USA

Abstract A dual‐function photoelectrochemical (PEC) separation system is demonstrated for rare‐earth element (REE) recovery. The sustainable release of the captured REEs is promoted through the synergistic integration of a redox‐reaction for electrostatic repulsion, and in situ proton generation for ion‐exchange, all driven by photoelectrochemistry. The platform consists of a redox‐copolymer, poly(ferrocenylpropyl methacrylamide‐ co ‐methacrylic acid) (P(FPMAm‐ co ‐MAA)) (PFM), conjugated with carbon nanotubes (CNTs) and coated onto titanium dioxide nanorods (TNRs). The (PFM‐CNT)/TNR spontaneously adsorbs up to 214.2 mg of Yttrium/g PFM by ion‐exchange, and demonstrates broad applicability for other REEs. The adsorbed REEs are released through the PEC oxidation of ferrocene (Fc) to ferrocenium (Fc ⁺ ), and the simultaneous PEC water splitting reactions at the TNRs that protonate the carboxylate binding groups. This dual photoelectrochemically‐driven mechanism for REE release is investigated by in situ pH measurements, as well as vibrational and X‐ray photoelectron spectroscopy. Through PEC approaches, a 68.8% reduction in energy consumption during REE recovery has been achieved compared to purely electrochemical systems, with a regeneration efficiency close to 100%. For NdFeB magnets from waste hard disk drives, Nd and Dy recovery efficiencies of 59.2 and 61.1% are achieved. The dual‐functionality of these copolymer PEC systems offers a sustainable platform for modulating critical element recovery.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0025636

OSTI ID:: 2567693

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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