Plasmon‐Switched Kinetics for Formic Acid Dehydrogenation: Selective Adsorption Driven by Local Field and Hot Carriers

Understanding illumination‐mediated kinetics is essential for catalyst design in plasmon catalysis. Here we prepare Pd‐based plasmonic catalysts with tunable electronic structures to reveal the underlying illumination‐enhanced kinetic mechanisms for formic acid (HCOOH) dehydrogenation. We demonstrate a kinetic switch from a competitive Langmuir‐Hinshelwood adsorption mode in dark to a non‐competitive type under irradiation triggered by local field and hot carriers. Specifically, the electromagnetic field induces a spatial‐temporal separation of dehydrogenation‐favorable configurations of reactant molecule HCOOH and HCOO− due to their natural different polarities. Meanwhile, the generated energetic carriers can serve as active sites for selective molecular adsorption. The hot electrons act as adsorption sites for HCOOH, while holes prefer to adsorb HCOO−. Such unique non‐competitive adsorption kinetics induced by plasmon effects serves as another typical characteristic of plasmonic catalysis that remarkably differs from thermocatalysis. This work unravels unique adsorption transformations and a kinetic switching driven by plasmon nonthermal effects. We observed that the kinetics of plasmon‐enhanced formic acid (FA)/sodium formate (SF) dehydrogenation can be distinct from that of thermal‐driven and successfully correlated this plasmon‐switched feature with the influence of local field/hot carriers on the microscopic adsorption behaviour of reactants.