Here, we present oxygen-deficient black ZrO2−x as a new material for sunlight absorption with a low band gap around ~1.5 eV, via a controlled magnesiothermic reduction in 5% H2/Ar from white ZrO2, a wide bandgap(~5 eV) semiconductor, usually not considered for solar light absorption. It shows for the first time a dramatic increase in solar light absorbance and significant activity for solar light-induced H2 production from methanol-water with excellent stability up to 30 days while white ZrO2 fails. Generation of large amounts of oxygen vacancies or surface defects clearly visualized by the HR-TEM and HR-SEM images is the main reason for the drastic alteration of the optical properties through the formation of new energy states near valence band and conduction band towards Fermi level in black ZrO2−x as indicated by XPS and DFT calculations of black ZrO2−x. Current reduction method using Mg and H2 is mild, but highly efficient to produce solar light-assisted photocatalytically active black ZrO2−x.
This study establishes big data for the catalytic properties of two-dimensional metal-dichalcogenides (2D-TMDs) toward the hydrogen evolution reaction (HER). In addition to conventionally known active sites of edges, it proposes that terrace sites (or the basal plane) can be substantially activated for the HER.
The identification and development of efficient catalysts made of non-precious materials for oxygen reduction reaction (ORR) are essential for the successful operation of a wide range of energy devices. This study provides evidence that earth-abundant nanoparticles of transition metals encapsulated in a nitrogen-doped carbon shell (M@N-C, M = Fe, Co, Ni, Cu or Fe alloys) are promising catalysts in acidic solutions. By density functional theory calculations and experimental validations, we quantitatively propose a method of tuning the ORR activity of M@N-C by controlling the nitrogen-doping level, the thickness of the N-C shells and binary alloying. FeCo@N-C/KB was chosen as the best ORR catalyst because of its onset and half-wave potentials of 0.92 and 0.74 V vs a reversible hydrogen electrode (RHE), respectively, and its excellent durability. Furthermore, FeCo@N-C/KB possesses a high activity for the hydrogen evolution reaction (HER; − 0.24 V vs RHE at − 10 mA cm − 2 ), thus demonstrating that it is a good bi-functional ORR and HER catalyst in acidic media.
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