As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm−2 and long-term durability in reversible zinc–air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.

Crystal phase regulations may endow materials with enhanced or new functionalities. However, syntheses of noble metal-based allomorphic nanomaterials are extremely difficult, and only a few successful examples have been found. Herein, we report the discovery of hexagonal close-packed Pt–Ni alloy, despite the fact that Pt–Ni alloys are typically crystallized in face-centred cubic structures. The hexagonal close-packed Pt–Ni alloy nano-multipods are synthesized via a facile one-pot solvothermal route, where the branches of nano-multipods take the shape of excavated hexagonal prisms assembled by six nanosheets of 2.5 nm thickness. The hexagonal close-packed Pt–Ni excavated nano-multipods exhibit superior catalytic property towards the hydrogen evolution reaction in alkaline electrolyte. The overpotential is only 65 mV versus reversible hydrogen electrode at a current density of 10 mA cm−2, and the mass current density reaches 3.03 mA μgPt−1 at −70 mV versus reversible hydrogen electrode, which outperforms currently reported catalysts to the best of our knowledge.

No abstract

No abstract