Unravelling Adsorbate–Metal–Oxide Interactions: Water Vapor Chemistry on the Growth and Sintering of Ni over Reducible CeO2(111) Thin Films

The role of water in the growth and sintering of Ni particles over well-ordered CeO_x(111) (1.5 < x < 2) thin films was investigated through scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) studies, considering ceria-supported Ni attracts great attention as a promising catalyst for reactions such as steam reforming of ethanol and water gas shift reaction, in which water vapor is used as a key reactant. In the study, both fully oxidized CeO₂ and partially reduced CeO_1.75 thin films were prepared to examine the effect of the oxygen vacancies/Ce³⁺ sites in ceria supports. Our STM results revealed that dosing water before or after Ni deposition over the CeO_x(111) surfaces at room temperature influenced the sintering behavior of Ni nanoparticles with further heating. Exposure of water to Ni nanoparticles that were deposited over both CeO₂ and CeO_1.75 at 300 K causes the formation of flatter particles with significantly reduced height when heating to the same temperatures compared to Ni/ceria with no water adsorbates. The flatter Ni particles were also observed when water was first dosed over CeO₂ at 300 K followed by Ni deposition at room temperature and further heating. Over a partially reduced CeO_1.75 surface with predosed water at 300 K, there is an extensive decrease in the particle density upon subsequent Ni deposition at room temperature and a significant increase in the height for Ni nanoparticles with further heating to higher temperatures compared to Ni over a pristine CeO_1.75 surface. This is due to the filling of oxygen vacancies caused by the dissociation of water. This creates fewer nucleation sites for Ni on ceria, weakening the metal–oxide interaction and causing significant metal sintering. Our experimental findings suggest distinct adsorbate–metal–oxide interactions are key to the tuning of sintering of Ni nanoparticles over the CeO_x(111) surface caused by water exposure. Such interactions are essential for the further modification of Ni-based catalysts for improved reactivity and stability.