Dual-Atom P-Co-Dy Charge-Transfer Bridge on Black Phosphorus for Enhanced Photocatalytic CO₂ Reduction

The synergistic effect of rare earth single-atoms and transition metal single-atoms may enable us to achieve some unprecedented performance and characteristics. Here, Co-Dy dual-atoms on black phosphorus with a P-Co-Dy charge-transfer bridge are designed and fabricated as the active center for the CO₂ photoreduction reaction. The synergistic effect of Co-Dy on the performance of black phosphorus is studied by combining X-ray absorption spectroscopy, ultrafast spectral analysis, and in situ technology with DFT calculations. The results show that the Co and Dy bimetallic active site can promote charge transfer by the charge transfer bridge from P to Dy, and then to Co, thereby improving the photocatalytic activity of black phosphorus. The performance of catalysts excited at different wavelength light indicates that the ⁴G_11/2/²I_15/2/⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 emissions of Dy can be absorbed by black phosphorus to improve the utilization of sunlight. The in situ DRIFTS and density functional theory (DFT) calculations are used to investigate the CO₂ photoreduction pathway. This work provides an depth insight into the mechanism of dual-atom catalysts with enhanced photocatalytic performance, which helps to design novel atomic photocatalysts with excellent activity for CO₂ reduction reactions.