In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO₂ Catalyst: Importance of Strong Metal–Support Interactions for the Cleavage of O–H Bonds

TLDR

Water dissociation is essential for many catalytic reactions on oxide‑supported transition‑metal catalysts. This study investigates how the ceria support influences O–H bond cleavage activity in nickel/ceria systems using experimental and DFT approaches. The enhanced activity arises from ceria’s ability to stabilize oxidized Ni(2+) species by localizing electrons in f‑states, which lowers the activation barrier for water dissociation. Ni/CeO₂ exhibits a higher OH coverage and lower activation barriers than bare CeO₂ or Ni₄ particles, leading to faster water dissociation that markedly improves the catalyst’s activity and stability for the water‑gas shift and ethanol steam‑reforming reactions.

Abstract

Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Supported by experimental and density-functional theory results, the effect of the support on OH bond cleavage activity is elucidated for nickel/ceria systems. Ambient-pressure O 1s photoemission spectra at low Ni loadings on CeO2 (111) reveal a substantially larger amount of OH groups as compared to the bare support. Computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO2 (111) compared with pyramidal Ni4 particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni(2+) species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO2 has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.