Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni(1-x)Fe(x)OOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe(3+) in Ni(1-x)Fe(x)OOH occupies octahedral sites with unusually short Fe-O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni(1-x)Fe(x)OOH are not active sites for the oxidation of water.

Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease the amount of platinum required, for example by alloying, but without detrimentally affecting its properties. The alloy PtxY is known to be active and stable, but its synthesis in nanoparticulate form has proved challenging, which limits its further study. Herein we demonstrate the synthesis, characterization and catalyst testing of model PtxY nanoparticles prepared through the gas-aggregation technique. The catalysts reported here are highly active, with a mass activity of up to 3.05 A mgPt(-1) at 0.9 V versus a reversible hydrogen electrode. Using a variety of characterization techniques, we show that the enhanced activity of PtxY over elemental platinum results exclusively from a compressive strain exerted on the platinum surface atoms by the alloy core.

Sodium-ion batteries have become a subject of increasing interest and are considered as an alternative to the ubiquitous lithium-ion battery. To compare the effect of two improvement strategies for metal oxide cathodes, specifically Codoping and morphology optimization, four representatives of the prominent material class of layered Na x MO 2 (M = transition metal) have been studied: hexagonal flakes and hollow spheres of P2− Na x MnO 2 and P2−Na x Co 0.1 Mn 0.9 O 2 . The better electrochemical performance of the spheres over the flakes and of the Co-doped over the undoped materials are explained on the basis of structural features revealed by operando synchrotron X-ray diffraction. The higher cycling stability of the material doped with ∼10% Co is attributed to three effects: (i) the suppression of a Jahn−Tellerinduced structural transition from the initial hexagonal to an orthorhombic phase that is observed in Na x MnO 2 ; (ii) suppression of ordering processes of Na + ; and (iii) enhanced Na + kinetics as revealed by galvanostatic intermittent titration technique measurements and in situ electrochemical impedance measurements. Increased capacity and cycling stability of spheres over flakes may be related to smaller changes of the unit cell volume of spheres and thus to reduced structural stress. Co-doped spheres combine the advantages of both strategies and exhibit the best cycling stability.