Mesoporous NiCo based nanowire arrays supported on three-dimensional N-doped carbon foams as non-noble catalysts for efficient oxygen reduction reaction

• Homologous NiCo based nanowire arrays grow on nitrogen-doped carbon foams.
• NiCo2O4 nanowires exhibit mesoporous structures composed of numerous nanoparticles.
• NiCo2S4 nanowires possess hollow structures with mesoporous walls.
• Homologous NiCo based composites exhibit excellent catalytic performance for ORR.

Homologous NiCo based mesoporous nanowire arrays, involving nickel cobalt oxide (NiCo2O4) and nickel cobalt sulfide (NiCo2S4), are successfully grown on three-dimensional (3D) nitrogen-doped carbon foam (NDCF) via a facile hydrothermal reaction followed by annealing and sulfurization treatment, respectively. The NiCo2O4 nanowires in the obtained NiCo2O4/NDCF composites are composed of numerous small nanoparticles with the presence of mesopores, while the NiCo2S4 nanowires of NiCo2S4/NDCF composites exhibit unique hollow structures with mesoporous walls. When served as non-noble catalysts for oxygen reduction reaction (ORR), the homologous NiCo2O4/NDCF and NiCo2S4/NDCF composites exhibit a comparable catalytic activity with a four-electron pathway, superior selectively and methanol tolerance over commercial Pt/C catalyst. Especially, the NiCo2S4/NDCF composites possess much higher stability than the Pt/C catalyst in alkaline electrolyte, thus holding great promise in practical application. The impressive performance may originate from the hollow nanowire morphology and the unique mesoporous structure which provide a high surface density of catalytic active sites exposed to oxygen molecules and facilitate the efficient transport of reactant species. Meanwhile, the introduced NDCF with enhanced catalytic activity from the incorporation of the N element generates synergistic effect with NiCo2O4 and NiCo2S4, and enhances their conductivities, therefore playing a significant role in improving their catalytic performance.

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