Ce-induced synergistic effect in exsolved perovskite catalyst for highly efficient and robust methane dry reforming.

Hao, Chencun; Qu, Zhiyu; Smith, Louise R; Dummer, Nicholas F; Qi, Haifeng; Slater, Thomas J A; Zhu, Zhiping; Zhang, Riguang et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Dry reforming of methane is an effective approach to convert two major greenhouse gases, methane and carbon dioxide, into high-value syngas, used as a feedstock for bulk and fine chemical synthesis. However, catalyst deactivation and carbon deposition under harsh conditions hinder its industrialization process. Herein, we present a Ce-modified and Ni-exsolved perovskite catalyst, 0.2Ce-La<sub>0.97</sub>Ni<sub>0.4</sub>Cr<sub>0.6</sub>O<sub>3</sub>, for achieving highly efficient and robust CH<sub>4</sub>-CO<sub>2</sub> reforming with CH<sub>4</sub> and CO<sub>2</sub> conversions of 87.4% and 92.9% at 800 °C, respectively. Moreover, this unique catalyst exhibits remarkable stability, maintaining its superior activity over 800 h. Characterization and density functional theory reveal that two Ce species are present: surface oxygen vacancy-moderate CeO<sub>2-x</sub> (Ce<sub>surf</sub>) and bulk lattice Ce (Ce<sub>bulk</sub>). These play a specific role in methane dry reforming, where the Ce<sub>surf</sub> promotes CO<sub>2</sub> adsorption and hinders carbon deposition, while Ce<sub>bulk</sub> induces lattice strain and Ni exsolution, key factors contributing to the high activity and stability.