Modulate the metallic Sb state on ultrathin PdSb-based nanosheets for efficient formic acid electrooxidation

Incorporation of oxophilic metals into Pd-based nanostructures has shown great potential in small molecule electrooxidation owing to their superior anti-poisoning capability. However, engineering the electronic structure of oxophilic dopants in Pd-based catalysts remains challenging and their impact on electrooxidation reactions is rarely demonstrated. Herein, we have developed a method for synthesizing PdSb-based nanosheets, enabling the incorporation of the Sb element in a predominantly metallic state despite its high oxophilic nature. Moreover, the Pd₉₀Sb₇W₃ nanosheet serves as an efficient electrocatalyst for the formic acid oxidation reaction (FAOR), and the underlying promotion mechanism is investigated. Among the as-prepared PdSb-based nanosheets, the Pd₉₀Sb₇W₃ nanosheet exhibits a remarkable 69.03% metallic state of Sb, surpassing the values observed for the Pd₈₆Sb₁₂W₂ (33.01%) and Pd₈₃Sb₁₄W₃ (25.41%) nanosheets. X-ray photoelectron spectroscopy (XPS) and CO stripping experiments confirm that the Sb metallic state contributes the synergistic effect of their electronic and oxophilic effect, thus leading to an effective electrooxidation removal of CO and significantly enhanced FAOR electrocatalytic activity (1.47 A mg^-1; 2.32 mA cm^-1) compared with the oxidated state of Sb. This work highlights the importance of modulating the chemical valence state of oxophilic metals to enhance electrocatalytic performance, offering valuable insights for the design of high-performance electrocatalysts for electrooxidation of small molecules.