In‐Plane Palladium and Interplanar Copper Dual Single‐Atom Catalyst in Bulk‐Like Carbon Nitride for Cascade CO2 Photoreduction

Dual single-atom catalysts (DSACs) are promising for breaking the scaling relationships and ensuring synergistic effects compared with conventional single-atom catalysts (SACs). Nevertheless, precise synthesis and optimization of DSACs with specific locations and functions remain challenging. Herein, dual single-atoms are specifically incorporated into the layer-stacked bulk-like carbon nitride, featuring in-plane three-coordinated Pd and interplanar four-coordinated Cu (Pd₁-Cu₁/b-CN) atomic sites, from both experimental results and DFT simulations. Using femtosecond time-resolved transient absorption (fs-TA) spectroscopy, it is found that the in-plane Pd features a charge decay lifetime of 95.6 ps which is much longer than that of the interplanar Cu (3.07 ps). This finding indicates that the in-plane Pd can provide electrons for the reaction as the catalytically active site in both structurally and dynamically favorable manners. Such a well-defined bi-functional cascade system ensures a 3.47-fold increase in CO yield compared to that of bulk-like CN (b-CN), while also exceeding the effects of single Pd₁/b-CN and Cu₁/b-CN sites. Furthermore, DFT calculations reveal that the inherent transformation from s-p coupling to d-p hybridization between the Pd site and CO₂ molecule occurs during the initial CO₂ adsorption and hydrogenation processes and stimulates the preferred CO₂-to-CO reaction pathway.