Dual-Atom Dopants Activated Copper Dilute Alloy Boosts Electroreduction CO₂-to-C₂₊ Products at Ampere-Level Current Density

Electrochemical CO₂ reduction reaction (CO₂RR) with H₂O as the hydrogen donor provides a sustainable and green route to product energy-dense multi-carbon (C₂₊) products, but guiding selectivity remains challenging due to competing pathways. Here, we construct atomic Al and Zn into nanoporous Cu to regulate the adsorption energies of *CO and *H intermediates. Efficient electrosynthesis of C₂₊ products from CO₂RR are achieved, delivering a Faradaic efficiency approaching 91.4%, a partial current density of −1.5 A cm⁻², and a C₂₊/C₁ ratio up to 26.9 in gas-fed flow cells. Experimental and theoretical studies reveal that the Al₁─Cu sites preferentially promote CO₂ activation, while Zn₁─Cu sites facilitate H₂O dissociation to ensure intermediate hydrogenation, thus synergistically driving the conversion of *CO to *CHO and promoting asymmetric *CHO─*CO coupling to form C₂₊ products on Cu site. This work establishes a dual-atom alloy that enhances proton supply to CO₂ and intermediates while regulating *CO coverage, providing a rational design concept for electrocatalysts toward the selective reduction of CO₂ to C₂₊ products.