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Hierarchical 3D Architectured Ag Nanowires Shelled with NiMn-layered Double Hydroxide as an Efficient Bifunctional Oxygen Electrocatalyst
S. A. Chala, M.-C. Tsai*, W.-N. Su*, K. B. Ibrahim, B. Thirumalraj, T.-S. Chan, J.-F. Lee, H. Dai*, and B.-J. Hwang*
Herein, we report hierarchical 3D NiMn-layered double hydroxide (NiMn-LDHs) shells grown on conductive silver nanowire (Ag NWs) cores as efficient, low-cost, and durable oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysts for metal–air batteries. The hierarchical 3D architectured Ag NW@NiMn-LDH catalysts exhibit superb OER/ORR activities in alkaline conditions. The outstanding bifunctional activities of Ag NW@NiMn-LDHs are essentially attributed to increasing both site activity and site populations. The synergistic contributions from the hierarchical 3D open-pore structure of the LDH shells, improved electrical conductivity, and small thickness of the LDHs shells are associated with more accessible site populations. Moreover, the charge transfer between Ag cores and metals of LDH shells and the formation of defective and distorted sites (less coordinated Ni and Mn sites) strongly enhance the site activity. Thus, Ag NW@NiMn-LDH hybrids exhibit a 0.75 V overvoltage difference between ORR and OER with excellent durability for 30 h, demonstrating the distinguished bifunctional electrocatalyst reported to date. Interestingly, the homemade rechargeable Zn–air battery using the hybrid Ag NW@NiMn-LDHs (1:2) catalyst as the air electrode exhibits a charge–discharge voltage gap of ∼0.77 V at 10 mA cm–2 and shows excellent cycling stability. Thus, the concept of the hierarchical 3D architecture of Ag NW@NiMn-LDHs considerably advances the practice of LDHs toward metal–air batteries and oxygen electrocatalysts.