Selectivity regulation of CO2 photoreduction via the electron configuration of active sites on single-atom photocatalysts

The major challenge in the photocatalytic reduction of CO2 is to achieve high conversion efficiency while maintaining selectivity for a single product. Photocatalysts containing single-metal Cu2+ with 3d9 and Zn2+ with 3d10 on g-C3N4 were prepared using a high-energy ball mill. Single-atom Zn inner electron configuration is stable (3d10) and the peripheral empty orbitals act as electron traps to trap photo-generated electrons and improve the efficiency of charge separation; Zn is an active site to enhance the adsorption and activation of CO2. The stable electron configuration can reduce the energy required for the overall reaction and increase the activity while changing the reaction pathway to form CO. As a result, the 0.5 mol% Zn/g-C3N4 (Zn-CN-0.5) photocatalyst achieves -100 % selectivity for the photocatalytic reduction of CO2 to CO at a rate of -21.1 mu mol & sdot;g  1 & sdot;h  1. In contrast, the 0.5 mol% Cu/g-C3N4 (Cu-CN-0.5) photocatalyst with an unstable electronic structure does not exhibit high selectivity.