Red Phosphorus Facilitates Single Metal Coordination: A Broadly Applicable Platform for Highly Selective CO 2 ‐to‐Ethylene Photocatalysis

Selective photocatalytic CO 2 ‐to‐C 2 H 4 conversion remains highly challenging because efficient C–C coupling is rarely achieved. Even when it is accomplished, it typically relies on delicate tailoring of metallic sites. Here, we demonstrate that red phosphorus (RP) can serve as an effective platform for feasible metal coordination, enabling highly selective C 2 H 4 production. Using Pt as a model (but not limited to Pt), we construct a single‐atom Pt‐P architecture on RP that achieves a C 2 H 4 production rate of 21.03 µmol g −1 h −1 with a selectivity exceeding 93% under visible‐light. Mechanistic studies show that the coordinated surface P atoms serve as the primary active sites and cooperate with Pt to mediate a more accessible C–C coupling pathway toward C 2 H 4 formation, unlike conventional Pt‐centered catalysis that mainly yields C 1 products. Notably, this strategy is also applicable to Co, Ni, Ag, Fe, Ir, Cu, Rh, and Pd, establishing RP as a broadly applicable coordination platform for selective CO 2 ‐to‐C 2 H 4 photocatalysis across a wide range of metals featuring only single‐metal sites.