Histidine‐Based “Transfer Stations” at Carbon‐Immobilized Metal Particles Enable Rapid Hydrogen Transfer for Efficient Formic Acid Dehydrogenation

The interaction of surface metal species with the solution plays a key role in engineering heterogeneous catalytic processes. Herein, we present the facile synthesis of L‐histidine‐coordinated PdAg nanoparticles (4.03 ± 0.08 nm) anchored on pristine carbon supports (denoted as PdAg‐NH2/C) and their use for formic acid dehydrogenation (FAD). Significant acceleration of FAD related to the histidine is observed, and the enhancement mechanism is experimentally and theoretically investigated. The presence of L‐histidine at metal sites promotes rapid binding of formic acid molecules due to acid‐base interactions. The local enrichment of both proton and formate at the metal‐solution interfaces promotes the subsequent formate decomposition and hydride transfer to the metal surface. The as‐generated surface H species are more concentrated compared to the previously reported catalyst where the metal is loaded on an amino‐modified support, this enabling a significantly enhanced H2 production. The optimal Pd1Ag1‐NH2/C catalyst exhibits a high turnover frequency of 6493.5 h‐1 at 333 K based on the total amount of Pd, together with a H2 selectivity of 100%. This study emphasizes the critical role of optimizing local transport pathways near catalytic centers chemically and further provide insights to the rational development of heterogeneous catalysts for FAD technologies.