Dual‐Single‐Atom Tailoring with Bifunctional Integration for High‐Performance CO₂ Photoreduction

Single-atom photocatalysis has been demonstrated as a novel strategy to promote heterogeneous reactions. There is a diversity of monoatomic metal species with specific functions; however, integrating representative merits into dual-single-atoms and regulating cooperative photocatalysis remain a pressing challenge. For dual-single-atom catalysts, enhanced photocatalytic activity would be realized through integrating bifunctional properties and tuning the synergistic effect. Herein, dual-single-atoms supported on conjugated porous carbon nitride polymer are developed for effective photocatalytic CO₂ reduction, featuring the function of cobalt (Co) and ruthenium (Ru). A series of in situ characterizations and theoretical calculations are conducted for quantitative analysis of structure-performance correlation. It is concluded that the active Co sites facilitate dynamic charge transfer, while the Ru sites promote selective CO₂ surface-bound interaction during CO₂ photoreduction. The combination of atom-specific traits and the synergy between Co and Ru lead to the high photocatalytic CO₂ conversion with corresponding apparent quantum efficiency (AQE) of 2.8% at 385 nm, along with a high turnover number (TON) of more than 200 without addition of any sacrificial agent. This work presents an example of identifying the roles of different single-atom metals and regulating the synergy, where the two metals with unique properties collaborate to further boost the photocatalytic performance.