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.