Ordered PdBi Alloys for High‐Performance CO ₂ Electroreduction and Enhanced Formic Acid Selectivity

Abstract Electrocatalytic conversion of CO 2 to formic acid (HCOOH) represents a promising approach for storing renewable energy and addressing the challenges of hydrogen storage and transportation. Palladium (Pd) is the only known metal capable of achieving this process at nearly zero overpotential. However, its practical applications are severely limited by hydrogen evolution reaction (HER) competition and CO poisoning. Bimetallic alloys, especially intermetallics with ordered structures, offer an effective way to optimize performance due to their unique catalytic properties. Here, PdBi alloys are synthesized with ordered structures and adjustable ratios of active sites for efficient CO 2 electroreduction to HCOOH. The o ‐PdBi 2 alloy effectively suppresses both HER competition and CO production during the CO 2 reduction process, achieving ≈95% HCOOH selectivity across a wide range of current densities and excellent stability at industrial‐level current densities. Additionally, the ordered structure facilitates high selectivity maintenance while mitigating overpotential, resulting in a cell voltage of only 2.65 V at 200 mA cm −2 . These findings provide a pathway for the practical application of Pd‐based catalysts in CO 2 electroreduction.