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Spin-State Transition in Heterometal-Bridged Cu-MnN4 Motifs Overcomes Activity-Stability Trade-Off for Ultra-Stable
Defeng Qi1,2, Junhao Wang1, Youpeng Cui1
1State Key Laboratory of Advanced Materials for Intelligent Sensing, Key Laboratory of Organic Integrated Circuit, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin, China.
None:
Rechargeable zinc-air batteries (ZABs) are promising for sustainable energy storage but limited by the scarcity of efficient and durable oxygen reduction reaction (ORR) catalysts. Transition metal M-N4 single-atom catalysts, particularly Mn-N4, offer structural stability but face an activity-stability trade-off due to electronic rigidity. Herein, we overcoming this dilemma by modulating Mn spin state via incorporating an adjacent Cu atom to form a heterometallic Cu-MnN4 motif (CuMn/NC). Experiments and density functional theory calculations reveal that Cu induces electron reconfiguration, driving a spin transition of Mn from intermediate- to high-spin states. This transition enhances electron occupancy in Mn-O antibonding orbitals, optimizes oxygen intermediate adsorption, and lowers the energy barrier of the rate-determining step (*OH desorption) by over 30%. The CuMn/NC achieves an exceptional ORR half-wave potential of 0.892 V vs. RHE, surpassing benchmark Pt/C (∼47 mV) and current Mn-based catalysts (∼101 mV), while maintaining remarkable stability (>91.9% current retention after 32 h). ZABs. with CuMn/NC delivered a record peak power density (172.6 mW cm-2) and unprecedented cycling stability (>1000 h with negligible voltage decay). This study demonstrates that precise spin-state modulation via heterometallic coordination provides a fundamental strategy for designing high-performance, durable electrocatalysts.
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