The selection of oxide materials for catalyzing the oxygen evolution reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity—a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir25Os75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the activity-stability factor. On the basis of this metric, the nanoporous Ir/IrO2 morphology of dealloyed Ir25Os75 shows a factor of ~30 improvement in activity-stability factor relative to conventional iridium-based oxide materials, and an ~8 times improvement over dealloyed Ir25Os75 nanoparticles due to optimized stability and conductivity, respectively. We propose that the activity-stability factor is a key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

Doped carbon-based systems have been extensively studied over the past decade as active electrocatalysts for both the two-electron (2e-) and four-electron (4e-) oxygen reduction reaction (ORR). However, the mechanisms for ORR are generally poorly understood. Here we report an extensive experimental and first-principles theoretical study of the ORR at nitrogen-doped reduced graphene oxides (NrGO). We synthesize three distinct NrGO catalysts and investigate their chemical and structural properties in detail via X-ray photoelectron spectroscopy, infrared and Raman spectroscopy, high-resolution transmission electron microscopy and thin-film electrical conductivity. ORR experiments include the pH dependences of 2e-versus 4e-ORR selectivity, ORR onset potentials, Tafel slopes and H/D kinetic isotope effects. These experiments show very different ORR behavior for the three catalysts, both in terms of selectivity and the underlying mechanism which proceeds either via coupled proton-electron transfers (CPETs) or non-CPETs. Reasonable structural models developed from DFT rationalize this behavior. The key determinant between CPET vs. non-CPET mechanisms is the electron density at the Fermi level under operating ORR conditions. Regardless of the reaction mechanism or electrolyte pH, however, we identify the ORR active sites as sp2 carbons that are located next to oxide regions. This assignment highlights the importance of oxygen functional groups, while details of (modest) N-doping may still affect the overall catalytic activity, and likely also the selectivity, by modifying the general chemical environment around the active site. File list (2) download file view on ChemRxiv NrGO_ACS_Catal_updated.pdf (3.76 MiB) download file view on ChemRxiv NrGO_SI_ACS_Catal_updated.pdf (6.66 MiB)

Electrochemical water splitting is promising for utilizing intermittent renewable energy. The sluggish kinetics of the oxygen evolution reaction (OER), however, is a bottleneck in obtaining high efficiency. Only a few OER electrocatalysts have been developed for the use in acidic media despite the importance of a proton exchange membrane (PEM) water electrolyzer. IrO 2 is the only material that is both active and stable for the OER in highly corrosive acidic conditions. Herein, a facile and scalable synthesis of ultrathin IrO 2 nanoneedles is reported with a diameter of 2 nm using a modified molten salt method. The activity and durability for the OER are significantly enhanced on the ultrathin IrO 2 nanoneedles, compared to conventional nanoparticles. The ultrathin nanoneedles are successfully introduced to a PEM electrolyzer single cell with the enhanced cell performance.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.

Minimizing the use of Pt catalysts in proton exchange membrane fuel cells (PEMFC) is important, considering its high price and scarcity. Herein, we demonstrate novel catalysts for PEMFCs with exceptionally...

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