Structural Heredity in Catalysis: CO Self-Selective CeO Nanocrystals for Efficient Photothermal CO Hydrogenation to Methane.

The chemical inertness of CO molecules makes their adsorption and activation on a catalyst surface one of the key challenges in recycling CO into chemical fuels. However, the traditional template synthesis and chemical modification strategies used to tackle this problem face severe structural collapse and modifier deactivation issues during the often-needed post-processing procedure. Herein, a CO self-selective hydrothermal growth strategy is proposed for the synthesis of CeO octahedral nanocrystals that participate in strong physicochemical interactions with CO molecules. The intense affinity for CO molecules persists during successive high-temperature treatments required for Ni deposition. This demonstrates the excellent structural heredity of the CO self-selective CeO nanocrystals, which leads to an outstanding photothermal CH productivity exceeding 9 mmol h m and an impressive selectivity of >99%. The excellent performance is correlated with the abundant oxygen vacancies and hydroxyl species on the CeO surface, which create many frustrated Lewis-pair active sites, and the strong interaction between Ni and CeO that promotes the dissociation of H molecules and the spillover of H atoms, thereby greatly benefitting the photothermal CO methanation reaction. This self-selective hydrothermal growth strategy represents a new pathway for the development of effective catalysts for targeted chemical reactions.