High‐performance <scp>PdPb</scp> alloy for the simultaneous production of formic acid and <scp> H ₂ </scp>

Abstract Developing durable catalysts for the efficient production of formic acid and H 2 remains challenging. Herein, we report the green synthesis of PdPb alloy electrocatalysts via a solvent‐free microwave method for both formic acid and H 2 generation. For the anodic methanol oxidation reaction, PdPb alloy exhibits a remarkable mass activity of 1.08 A mg Pd −1 (15 times higher than Pd). In situ analysis and density functional theory calculations confirm that the alloy lowers the energy barrier of the non‐CO pathway with mitigated carbon monoxide (CO)* poisoning. For the cathodic H 2 evolution reaction, PdPb alloy promotes efficient H* formation and reduces the overpotential by 110 mV at 10 mA cm −2 . In the coupled system, only 1.49 V is required to achieve 10 mA cm −2 , simultaneously producing 84.4 mL of H 2 over 10 h, outperforming previously reported systems. This work highlights an efficient and durable alloy catalyst for the co‐production of high‐value chemicals and H 2 .