Structural Heredity in Catalysis: CO 2 Self-Selective CeO 2 Nanocrystals for Efficient Photothermal CO 2 Hydrogenation to Methane.

The chemical inertness of CO 2 molecules makes their adsorption and activation on a catalyst surface one of the key challenges in recycling CO 2 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 2 self-selective hydrothermal growth strategy is proposed for the synthesis of CeO 2 octahedral nanocrystals that participate in strong physicochemical interactions with CO 2 molecules. The intense affinity for CO 2 molecules persists during successive high-temperature treatments required for Ni deposition. This demonstrates the excellent structural heredity of the CO 2 self-selective CeO 2 nanocrystals, which leads to an outstanding photothermal CH 4 productivity exceeding 9 mmol h -1 m cat -2 and an impressive selectivity of >99%. The excellent performance is correlated with the abundant oxygen vacancies and hydroxyl species on the CeO 2 surface, which create many frustrated Lewis-pair active sites, and the strong interaction between Ni and CeO 2 that promotes the dissociation of H 2 molecules and the spillover of H atoms, thereby greatly benefitting the photothermal CO 2 methanation reaction. This self-selective hydrothermal growth strategy represents a new pathway for the development of effective catalysts for targeted chemical reactions.