Modulating Charge Accumulation via Electron Interaction for Photocatalytic Hydrogen Evolution: A Case of Fabricating Palladium Sites on ZnIn₂S₄ Nanosheets

It is desirable to regulate charge migration synergisticallyviaatomic level decoration because it can construct active sites withboth thermodynamic and kinetic advantages in photocatalytic hydrogen(H-2) evolution. Here, a mild cation exchange-mediated strategywas applied to anchor palladium (Pd) cations in the ZnIn2S4 nanostructure, achieving an outstanding H-2 evolution rate of 1236.4 & mu;mol h(-1) (& lambda;& GE; 420 nm) accompanied by an apparent quantum efficiency of60.06% (& lambda; = 420 nm). Pd dopants act as both active sites andsurface chemical state modulators, which help to balance *H adsorptionthermodynamically. More importantly, in situ electron spin resonanceand in situ XPS analysis reveal that the synergistic electron interactionbrought by the Pd-S structure constructs an efficient transferchannel, leading to more delocalized photocarriers to the active sitesfor H-2 evolution reaction. A feasible strategy is proposedin this study to improve the performance of photocatalysts from theviewpoint of Pd cation exchange. Simultaneously, synergistic electroninteraction is verified to modulate charge accumulation at Pd substitutionsites, providing substantiation and unique insights into the electronicstructure modification of photocatalysts.