Shape-tuned, surface-active and support-free silver oxygen reduction electrocatalyst enabled high performance fully...

Exploring non-platinum group metal (n-PGM) based efficient oxygen reduction reaction (ORR) electro-catalysts is highly important for realizing advancement in sustainable next generation-alkaline anion exchange membrane fuel cells (AAEMFCs). Herein, we demonstrate a new "hierarchical shape tuning approach" for the synthesis of controlled sized and shaped non-PGM based Ag ORR electro-catalysts with surface active nano-islands. Hierarchical shapes ranging from spherical (S-AgNs), worm-in-sphere, sphere-in-worm and vermiform (worm-like) Ag nanostructures (V-AgNs) were obtained by precisely varying the ratios of capping agent to dual reducing agents in water at ambient conditions. Compared to S-AgNs, V-AgNs revealed a higher mass normalized ORR Tafel activity (0.303 A mg_Ag ^-1 at 0.9 V), onset (1.06 V) and half wave (0.78 V) potentials and higher retention of limiting current density (>88%) after 5000 cycles in 0.5 M potassium hydroxide (KOH) solution attributable to their unique worm like morphology with surface active nano-islands and support free-nature enabled better catalyst utilization. In a fully "non-PGM AAEMFC" (n-PAAEMFC), V-AgNs exhibited the highest fuel cell activity of 115.6 mW cm^-2 and stable short-term durability (∼240 h) compared to S-AgNs (41.3 mW cm^-2) and previously reported fully n-PAAEMFCs indicating their potential use in next-generation alkaline fuel cells.