One Beam, Dual Insights: Simultaneous Chemical and Structural Changes in Nanopatterned Ceria under Reaction Conditions

Ceria's interaction with hydrogen can proceed through multiple chemical forms (hydride, hydroxyl, and oxyhydroxide-like), with consequences for the oxidation state, density, and morphology that are rarely tracked in the same evolving state. Here we show that under mild H₂ (and H₂ and CO₂) environments nanopatterned ceria undergoes oxidation-state changes accompanied by hydrogen incorporation that increases the effective electron density, establishing the following order: CeO₂Hy > CeO₂ > CeO2-xHy > CeO2-x. In parallel, the surface roughens in a chemically specific manner, with the largest changes coinciding with conditions where incorporated hydrogen is driven to react with oxygen supplied either by air exposure between experiments or by added CO₂. We obtained these insights by using a single X-ray beam to simultaneously perform ambient-pressure X-ray photoelectron spectroscopy and grazing-incidence X-ray scattering on the same sample spot. Single-mode measurements can miss key ceria-H₂ transformations relevant to optimizing ceria-based hydrogenation catalysts and supports.