Mitigating H<sub>ad</sub> Binding Energy in Formate\nOxidation through Electron Translocation between Pd and ZrO<sub>2</sub>

Palladium metal catalysts have emerged as the preferred\nchoice\nfor alkaline formate oxidation reaction (FOR) due to their high activity.\nHowever, their strong binding with adsorbed H (H<sub>ad</sub>) allows\nH<sub>ad</sub> to occupy the active site, resulting in slow FOR kinetics.\nHerein, we developed a ZrO<sub>2</sub>/Pd/C catalyst to decrease the\nH<sub>ad</sub> binding strength on Pd active sites, thereby enhancing\nthe FOR in alkaline media. Through experimental investigations and\ndensity functional theory (DFT) calculations, we elucidated the relationship\nbetween the d-band center of Pd and hydrogen binding energy (HBE).\nOur findings reveal that electron transfer from ZrO<sub>2</sub> to\nPd, driven by the work function disparity, results in a downshift\nof the d-band center of Pd. This shift weakens the HBE at Pd active\nsites, facilitating the desorption of H<sub>ad</sub> intermediates\nand thereby improving catalytic efficiency. As a result, the ZrO<sub>2</sub>/Pd/C catalyst demonstrated a 2.8-fold increase in activity\nover commercial Pd/C, exhibiting a lower peak potential and a significantly\nhigher peak current of 1787 mA mg<sup>–1</sup>. This work advances\nour understanding of the interplay between electronic structure and\ncatalytic performance, setting a benchmark for high-performance electrocatalysts\nin energy conversion technologies.