Crystalline Ni5P4 evolves hydrogen with electrical-efficiency comparable to platinum—while being corrosion-resistant in both acid and base for >16 hours.

We report microcrystalline Ni3P as a noble-metal-free electrocatalyst for the H2 evolution reaction (HER) with high activity just below those of Ni5P4 and Pt, the two most efficient HER catalysts known. Ni3P has previously been dismissed for the HER, owing to its anticipated corrosion and its low activity when formed as an impurity in amorphous alloys. We observe higher activity of single-phase Ni3P crystallites than for other nickel phosphides (except Ni5P4) in acid, high corrosion tolerance in acid, and zero corrosion in alkali. We compare its electrocatalytic performance, corrosion stability, and intrinsic turnover rate to those of different transition-metal phosphides. Electrochemical studies reveal that poisoning of surface Ni sites does not block the HER, indicating P as the active site. Using density functional theory (DFT), we analyze the thermodynamic stability of Ni3P and compare it to experiments. DFT calculations predict that surface reconstruction of Ni3P (001) strongly favors P enrichment of the Ni4P4 termination and that the H adsorption energy depends strongly on the surface reconstruction, thus revealing a potential synthetic lever for tuning HER catalytic activity. A particular P-enriched reconstructed surface on Ni3P­(001) is predicted to be the most stable surface termination at intermediate P content, as well as providing the most active surface site at low overpotentials. The P adatoms present on this reconstructed surface are more active for HER at low overpotentials in comparison to any of the sites investigated on other terminations of Ni3P­(001), as they possess nearly thermoneutral H adsorption. To our knowledge this is the first time reconstructed surfaces of transition-metal phosphides have been identified as having the most active surface site, with such good agreement with the experimentally observed catalytic current onset and Tafel slope. The active site geometry achieved through reconstruction identified in this work shows great similarity to that reported for Ni2P­(0001) and Ni5P4(0001) facets, serving as a general design principle for the future development of even more active transition-metal phosphide catalysts and further climbing the volcano plot.

Using a combination of X-ray absorption spectroscopy experiments with first principle calculations, we demonstrate that insulating KCuO2 contains Cu in an unusually-high formal-3+ valence state, the ligand-tometal (O to Cu) charge transfer energy is intriguingly negative (∆ ∼ −1.5 eV) and has a dominant (∼60%) ligand-hole character in the ground state akin to the high Tc cuprate Zhang-Rice state. Unlike most other formal Cu 3+ compounds, the Cu 2p XAS spectra of KCuO2 exhibits pronounced 3d 8 (Cu 3+ ) multiplet structures, which accounts for ∼40% of its ground state wave-function. Ab initio calculations elucidate the origin of the band-gap in KCuO2 as arising primarily from strong intra-cluster Cu 3d -O 2p hybridizations (t pd ); the value of the band-gap decreases with reduced value of t pd . Further, unlike conventional negative charge-transfer insulators, the band-gap in KCuO2 persists even for vanishing values of Coulomb repulsion U , underscoring the importance of single-particle band-structure effects connected to the one-dimensional nature of the compound.