Electrophile-Nucleophile Paired Heteronuclear Dual-Site for Selective CO₂ Photoreduction to Ethanol via...

Photocatalytic CO₂ reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C-C coupling and competitive C-O cleavage toward ethylene. Herein, an electrophile-nucleophile pairing strategy is developed by constructing atomically Cu-Zr heteronuclear dual sites within a porphyrinic framework, which can simultaneously reduce repulsion for C-C coupling and strengthen the C-O bond. The electron-deficient Zr, as a strong oxygen-affixed anchor, stabilizes critical *OCH intermediates via O-coordination, while adjacent electron-rich Cu sites drive *CO adsorption-inducing charge asymmetry between *OCH and *CO for kinetically favored dimerization. Subsequent hydrogenation selectively proceeds toward ethanol due to enhanced Zr-O stabilization that prevents C-O scission. The optimized catalyst achieved a near-unity ethanol selectivity at 87.8 µmol·g^-1·h^-1 using water as a scavenger under a CO₂ pressure of 0.5 MPa, which further increased to 195.1 µmol·g^-1·h^-1 at 1.5 MPa. This work establishes mismatched electrophile-nucleophile pairs as a versatile design principle for steering photocatalytic CO₂ reduction toward value-added multicarbon products.