Investigating Ni nanoparticles on CeO₂ for methane dissociation: a comparative study of theoretical calculations and experimental insights

CeO₂ supported with Ni nanoparticles has emerged as a promising catalyst for enhancing the efficiency of dry reforming of methane (DRM) reaction. Methane dissociation (CH₄ → CH₃ + H) was reported as one of the rate-determining steps in the DRM reaction. We elucidated the reaction mechanism and explored methods for reducing the activation energy using density functional theory (DFT) calculations, where the activation energy of methane dissociation was determined at multiple Ni₄ cluster sites on CeO₂. In parallel, we experimentally evaluated methane dissociation based on the methane consumption rate in the DRM reaction using newly developed flower-like Ni-supported CeO₂ catalyst (Ce(F)). The experimental activation energy was determined to be 0.69 eV (15.91 kcal mol^-1), closely matching the DFT-calculated value of 0.80 eV (18.45 kcal mol^-1) for the Ni₄ cluster model, validating our theoretical predictions. Additionally, we discovered that positively charging the Ni₄ can lower the activation energy of methane dissociation. These findings contribute to a deeper understanding of how to control the activation energy of the methane dissociation reaction in DRM.