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We report that the Co 3 O 4 nanoparticle‐mediated electrochemical oxidation under alkaline conditions of hydroxide ion on a glassy carbon macroelectrode leads to hydrogen peroxide as the initial oxidation product of electron transfer. The latter is inferred to subsequently partially decompose to dioxygen by catalytic chemical reaction at the nanoparticles. At the single particle level, electrochemical particle‐electrode impacts point out the rate‐determining step and the limiting kinetics of the reaction. Further, particles with core‐shell structure of a Co 3 O 4 core and SiO 2 shell are synthesised, and their electrochemical behaviour is studied and compared with bare Co 3 O 4 nanoparticles, suggesting the very likely broken or highly porous state of the silica shell, which is not otherwise easily distinguished, for example by electron microscopy.

We optimized the syntheses of α- and β-Bi4I4 and transferred the method to the very bismuth-rich iodides Bi14I4, Bi16I4, and Bi18I. Phase-pure, microcrystalline powders of BimI4 (m = 4, 14, 18) can now by synthesized on a multigram scale. Conditions for the growth of single crystals of Bi16I4 and Bi18I4 were determined. The redetermination of the crystal structure of Bi16I4 hints at a stacking disorder or the presence of 1͚[BimI4] ribbons with m = 14 and 18 among the dominant type along with m = 16. The electronic band structures for m = 14, 16, and 18 were calculated including spin-orbit coupling. They vary markedly with m and show numerous bands crossing the Fermi level, predicting a 3D-metallic behavior. Measurements of the electrical resistivity of a polycrystalline sample of Bi14I4 as well as polycrystalline and single-crystalline samples of Bi18I4 confirmed their metallic nature over the temperature range 300 K to 2 K. For BiI4, a positive and strictly linear magnetoresistance at 2 K in static magnetic fields up to 14 T was observed, which could indicate a topologically nontrivial electronic state.