Multi-shell Au@Rh nanoantenna reactor with collective plasmonic excitation for photothermal CO_(2)methanationOA

The photothermal pathway for converting carbon dioxide(CO_(2))into hydrocarbons presents an effective and straightforward production for solar fuels.Nonetheless,the rational design of a robust solar-driven catalytic system for efficient CO_(2)conversion remains a persistent challenge.In this work,we elaborately construct a multi-shell Au@Rh nanoantenna reactor for photothermal CO_(2)methanation.The plasmonically active multi-shell Au structure serves as“antenna”,and the catalytically active Rh nanoparticles function as“reactor”.The reactor exhibits a superior CH_(4) yield rate and nearly 100% selectivity,in comparison with the other Au structures(single-shell(SS)and nanoparticle)and the kinds of active sites(Ru,Ir,and Co).The well-arranged Au nanoparticles in multi-shell structure provide the collective plasmon-coupled excitation,leading to the strong localized surface plasmon resonance(LSPR)effect.Then,the antenna could convert the wide-spectrum solar energy to high surface temperature and enhanced electric field.The in-situ spectra and theoretical calculation indicate that the CO_(2)methanation reaction in Au@Rh nanoantenna reactor follows the formyl pathway.The strong electron-proton coupling transfer ability of Au@Rh nanoantenna reactor contributes to the complex reaction pathway for CO_(2)methanation.Especially,compared with Au catalyst,both the formation of intermediate and the key transformation from to in Au@Rh nanoantenna reactor were promoted through the adequate supply of proton-electron pair and the strong interaction between Au and Rh sites.The ingenious design for nanoantenna reactor and the new findings in photothermal CO_(2)methanation will inspire the development of mild hydrogenation for boosting CO_(2)-to-fuel conversion.