Efficient Photogenerated Carrier‐Assisted CO_ads Removal via Schottky Barrier of PdSn/WO₃ for Formic Acid Oxidation Reaction

Limiting the formation of CO adsorbed species (CO_ads) or promoting its removal during formic acid oxidation reaction (FAOR) is essential to improving the activity and stability of Pd-based catalysts. In this work, an innovative strategy is proposed to adjust the Schottky barrier height (SBH) through band structure design for effective utilization of photogenerated carriers to remove CO_ads, thereby improving the FAOR performance of Pd-based catalysts. Specifically, the electronic structure of Pd is adjusted by loading on the WO₃ nanosheets and incorporating different amounts of Sn to reduce Fermi level pinning and adjust SBH. The accelerated migration of photogenerated electrons promotes the accumulation of photogenerated holes on the valence band of WO₃ for the oxidation and removal of CO_ads. The constructed Schottky barrier effectively regulates the electronic structure of the catalyst and optimizes the adsorption energy of intermediate CO, thus inhibiting the indirect reaction pathway. Therefore, the optimal Pd₁Sn₁/WO₃ catalyst provides higher CO_ads removal efficiency for photogenerated carrier-assisted electrocatalytic FAOR, with a mass activity of 2262.3 mA mg^-1 _Pd, outperforming most Pd-based catalysts. This work offers a novel approach to designing Pd-based catalysts, combining electronic structure modulation with photogenerated carrier assistance for the effective removal of CO_ads to advance FAOR performance.