Ligand-Driven Tuning of Adsorption Energy in Nanocrystals for High-Performance H 2 O 2 Electrosynthesis

Surface ligands modulate the electronic structure of nanocrystals (NCs); however, in catalytic applications, these ligands are often removed due to concerns about blocking active sites. We studied herein whether ligand functionality and a judiciously chosen degree of ligand coverage can precisely tune the adsorption energy of key intermediates on NC catalysts. Guided by density functional theory calculations, we introduced electron-withdrawing ligands at an optimized coverage on Ag 2 S NCs, achieving an ideal balance in intermediate adsorption strength (Δ G OOH* = 4.16 eV). This turned Ag 2 S NCs─intrinsically inactive for the two-electron oxygen reduction reaction─into efficient H 2 O 2 electrocatalysts. When integrated onto oxidized carbon nanotube supports, these catalysts exhibited a stable H 2 O 2 production of 161 mg cm –2 h –1 with a Faradaic efficiency of 84% at 300 mA cm –2 in neutral media. This ligand-driven tuning strategy opens new avenues to control and enhance the catalytic properties of NCs.