Iron Triad-Based Bimetallic M-N-C Nanomaterials as Highly Active Bifunctional Oxygen Electrocatalysts.

The use of precious metal electrocatalysts in clean electrochemical energy conversion and storage applications is widespread, but the sustainability of these materials, in terms of their availability and cost, is constrained. In this research, iron triad-based bimetallic nitrogen-doped carbon (M-N-C) materials were investigated as potential bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synthesis of bimetallic FeCo-N-C, CoNi-N-C, and FeNi-N-C catalysts involved a precisely optimized carbonization process of their respective metal-organic precursors. Comprehensive structural analysis was undertaken to elucidate the morphology of the prepared M-N-C materials, while their electrocatalytic performance was assessed through cyclic voltammetry and rotating disk electrode measurements in a 0.1 M KOH solution. All bimetallic catalyst materials demonstrated impressive bifunctional electrocatalytic performance in both the ORR and the OER. However, the FeNi-N-C catalyst proved notably more stable, particularly in the OER conditions. Employed as a bifunctional catalyst for ORR/OER within a customized zinc-air battery, FeNi-N-C exhibited a remarkable discharge-charge voltage gap of only 0.86 V, alongside a peak power density of 60 mW cm-2. The outstanding stability of FeNi-N-C, operational for about 55 h at 2 mA cm-2, highlights its robustness for prolonged application.

Surface Curvature Effect on Dual-Atom Site Oxygen Electrocatalysis.

Improved oxygen electrocatalysis is crucial for the ever-growing energy demand. Metal-nitrogen-carbon (M-N-C) materials are promising candidates for catalysts. Their activity is tunable via varying electronic and geometric properties, such as porosity. Because of the difficulty in modeling porosity, M-N-Cs with variable surface curvature remained largely unexplored. In this work, we developed a realistic in-pore dual-atom site M-N-C model and applied density functional theory to investigate the surface curvature effect on oxygen reduction and evolution reactions. We show that surface curving tailors both scaling relations and energy barriers. Thus, we predict that adjusting the surface curvature can improve the catalytic activity toward mono- and bifunctional oxygen electrocatalysis.

Enhanced oxygen reduction reaction activity and durability of Pt nanoparticles deposited on graphene-coated alumina nanofibres.

The oxygen reduction reaction (ORR) activity and stability of Pt catalysts deposited on graphene-coated alumina nanofibres (GCNFs) were investigated. The GCNFs were fabricated by catalyst-free chemical vapour deposition. Pt nanoparticles (NPs) were deposited on the nanofibres by sonoelectrochemical and plasma-assisted synthesis methods. Scanning and transmission electron microscopy analyses revealed different surface morphologies of the prepared Pt catalysts, depending on the synthesis procedure. Sonoelectrochemical deposition resulted in a uniform distribution of smaller Pt NPs on the support surface, while plasma-assisted synthesis, along with well-dispersed smaller Pt NPs, led to particle agglomeration at certain nucleation sites. Further details about the surface features were obtained from cyclic voltammetry and CO stripping experiments in 0.1 M HClO4 solution. Rotating disk electrode investigations revealed that the Pt/GCNF catalyst is more active towards the ORR in acid media than the commercial Pt/C (20 wt%). The prepared catalyst also showed significantly higher durability than commercial Pt/C, with no change in the half-wave potential after 10 000 potential cycles.