Subnanometric Bismuth Clusters Confined in Pyrochlore-Bi2 Sn2 O7 Enable Remarkable CO2 Photoreduction.

Abstract

The development of highly efficient photocatalysts for conversion of carbon dioxide (CO2 ) with water (H2 O) into chemical fuels is of great importance for energy sustainability and carbon resource utilization. Herein, we demonstrated a facile hydrothermal method for in situ construction of subnanometric Bi metallic clusters in pyrochlore-Bi2 Sn2 O7 frameworks, leading to the remarkable improvements of photocatalytic performances for CO2 reduction into CO in the absence of sacrificial reagent. More specifically, an outstanding CO evolution activity of 114.1 μmol g-1 h-1 has been achieved, more than 20-fold improvement compared with the pristine Bi2 Sn2 O7 (5.7 μmol g-1 h-1 ). Detailed experiments together with in situ characterizations reveal that the spatially confined Bi clusters could significantly promote charge-separation/electron-enrichment and adsorption/activation of CO2 molecules, which provides highly efficient reaction channels to facilitate the generation of *COOH intermediate as well as the subsequent desorption of *CO towards CO formation. These demonstrations provide an important knowledge for precise design and fabrication of highly efficient photocatalysts for CO2 conversion into solar fuels.