Collaboration between Iridium Clusters and the {111} Dominant Facet of Cu2O for Triggering Efficient N2 Photofixation

The exploration of advanced photocatalysts for efficient N₂ reduction reaction (NRR) by integrating facet-engineering and realistic N₂ active sites is very promising, but it remains a challenge due to the absence of rational structural design and atomic-level insights into molecular N₂ activation. Herein, the same main group transition metal (e.g., Co, Rh, and Ir) clusters were ingeniously modified onto the dominant {111} crystal facet of Cu₂O nanocrystal, aiming to track the synergistic effect of various N₂ active sites and facet-engineering for efficient N₂ photofixation. Intriguingly, further theoretical studies reveal that the incorporating Ir clusters can improve light absorption ability, accelerate photogenerated charge separation and transfer, and lower the reaction energy barrier, thereby expressively promoting the real photoreactivity. The present work offers a promising approach to cooperatively regulate the facet-engineering and N₂ active centers at the atomic level, expecting to guide innovative design of smart NRR systems.