Angle-dependent hard X-ray photoemission study of Nb hydride formation in high-pressure supercritical water

• Nb hydrides in 10-GPa supercritical water are studied by photoelectron spectroscopy.
• The hydride components of the Nb 3d core-level spectra are increased with the depth.
• The bulk valence-band spectrum shows a split band due to the Nb–H bond formation.
• The hydrides are formed in the bulk and their surfaces are covered with Nb oxides.

Nb hydrides formation in 10-GPa supercritical water has been investigated by angle-dependent micro-beam hard X-ray photoemission spectroscopy. In the Nb 3d core-level spectra, Nb hydride components are found in the slightly high binding energy side of the metallic components, and the oxide ones are observed even though little oxides are recognized in X-ray diffraction patterns. Obtained emission-angle dependence of the Nb 3d core-level spectra of Nb hydride specimens shows that the Nb hydride components increase with the emission angle decreased i.e. the sampling depth increased, while the oxide ones decrease. The bulk valence-band spectrum is obtained by decomposing the measured valence-band spectra into a bulk and surface components with use of the emission-angle dependence of the core-level and valence-band spectra; it consists of two bands. This implies the Nb–H chemical bond formation and Nb in an oxidation state, consistent with reported band structure calculations and the observed core-level chemical shifts. Thus it is confirmed by valence-band and core-level photoelectron spectroscopy that the Nb hydrides are formed inside the specimen, irrespective to the well-known high oxidation ability of supercritical water.