Issue

Vol. 19 (2027)

Bioinspired Molecular Magnetic Field-Responsive Catalyst for On-Demand Switching of 2e− and 4e− Oxygen Reduction

https://doi.org/10.1007/s40820-026-02319-0
Boying Zhang
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Qiaoling Guo
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Haochuan Li
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Yue Wang
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Qing Li
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Haining Liu
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China
Shanlin Qiao
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People’s Republic of China

Corresponding Author: Shanlin Qiao

ccpeslqiao@hebust.edu.cn

Nano-Micro Letters, Vol. 19 (2027), Article Number: 26

Abstract

Achieving precise and on-demand steering of the oxygen reduction reaction (ORR) pathway between the efficient 4e− route to H2O and the valuable 2e− route to H2O2 remains a pivotal challenge in electrocatalysis. Herein, we address this challenge by designing a bioinspired molecular magnetic field-responsive catalyst (MMFR-C) via magnetic single-atom-anchored Salen-based covalent organic frameworks (MSA-Salen COFs) onto magnetic nanoparticles (single/multi-domain Fe3O4). Mimicking cytochrome c oxidase, the MMFR-C employs MSA-Salen COFs as an ordered proton-transfer channel and well-defined N2-M-O2 moieties as enzymatic O2 activation sites, with Fe3O4 providing a built-in magnetic field for remote regulation of the active-site electronic structure. The bioinspired MMFR-C exhibits switchable ORR pathways. Relative to the pristine Co-Salen COF (26% H2O2 selectivity, n = 3.48), the MMFR-C integrated with a single-domain Fe3O4 exhibits a remarkably enhanced H2O2 selectivity of 63.9% (n = 2.72), while that with a multi-domain Fe3O4 diverts the ORR pathway toward the 4e− route (n = 3.67). (i) We elucidate that the uniform magnetic field from the single-domain Fe3O4 in MMFR-C favors orbital hybridization between its active N2-M-O2 moieties and the *OOH intermediate, with moderate *OOH adsorption suppressing O–O scission and thus steering ORR selectivity toward H2O2. (ii) In contrast, the enhanced specific magnetism from its multi-domain Fe3O4 core optimizes the d-band center of MMFR-C’s active sites, stabilizes triplet O2 adsorption, and reduces spin-forbidden transition barriers, thereby facilitating O–O cleavage and diverting its ORR pathway to the 4e− route.


Highlights:
1 The bioinspired molecular magnetic field responsive catalysts were synthesized to selectively switch between the 2e− and 4e− oxygen reduction reaction (ORR) pathways.
2 The molecular magnetic field responsive catalyst integrated with single domain Fe3O4 delivers a significantly boosted H2O2 selectivity of 63.9% (electron transfer number, n = 2.72), whereas the multi domain Fe3O4 incorporated variant effectively redirects the ORR exclusively toward the 4e− pathw ay (n = 3.67).

Keywords

Molecular magnetic field-responsive catalyst Metal-Salen covalent organic frameworks Oxygen reduction reaction Selectivity regulation
Zhang, Boying, Qiaoling Guo, Haochuan Li, Yue Wang, Qing Li, Haining Liu, and Shanlin Qiao. 2026. “Bioinspired Molecular Magnetic Field-Responsive Catalyst for On-Demand Switching of 2e− and 4e− Oxygen Reduction”. Nano-Micro Letters 19 (August):26. https://doi.org/10.1007/s40820-026-02319-0.
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