The role of Copper–Ceria interactions in catalysis science: Recent theoretical and experimental advances

• Recent theoretical and experimental advances on Cu–Ceria interactions.
• Fundamental understanding and fine–tuning of Cu–Ceria interactions.
• Metal–support interactions and theirs implications in catalysis (WGS, PROX, SCR, etc).
• Role of surface defects, electronic perturbations and redox interplays on interfacial activity.
• Fine-tuning of local surface structure by synthesis routes and/or electronic promotion.

Copper-containing cerium oxide materials have received considerable attention both in catalysis and electro-catalysis fields due to their unique physicochemical characteristics in conjunction to their lower cost compared to noble metals (NMs)-based catalysts. Nowadays, it is well documented that the complex Copper–Ceria interactions (either geometric or electronic) have a key role on the catalytic performance. Hence, considerable efforts have been devoted on the understanding and the fine-tuning of metal–oxide interactions. Despite the growing progress in the field, several crucial issues related to the influence of: i) particle’s shape and size, ii) active site’s chemical state, iii) charge transfer between interfacial sites, and iv) intrinsic defects (e.g., surface oxygen vacancies) on the interfacial activity are still under investigation. This survey summarizes the recent advances in the last 10 years on the fundamental origin of Copper–Ceria interactions and their implications on the catalytic activity. The insights lately obtained by means of: i) ex situ advanced characterization techniques, ii) in situ sophisticated studies (e.g., operando techniques), iii) theoretical analysis (e.g., DFT calculations), and iv) innovative probing approaches (such as the inverse CeO2/CuO model system) are provided. The state-of-the-art catalytic applications of CuO/CeO2 binary oxides (water gas shift (WGS) reaction, preferential oxidation (PROX) of CO, CO2 hydrogenation, selective catalytic reduction (SCR), N2O decomposition, etc.) in relation to the aforementioned aspects are discussed. Some guidelines towards the fine-tuning of the surface chemistry of CuO/CeO2 catalysts for real life energy and environmental application are provided.

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