Histidine‐Based “Transfer Stations” at Carbon‐Immobilized Metal Particles Enable Rapid Hydrogen Transfer for Efficient Formic Acid Dehydrogenation
Zhenyi Yang, Guoyu Hou, Nana Gao, Yicheng Li, Xingqiu Li, Zitao Chen, Haibao Jin, Ming Zhao, Dongyang Wang, Ke Chen, Markus Antonietti, Tianxi Liu, Zhihong Tian, Yu Zhang
Abstract
Abstract 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‐NH 2 /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 protons 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 H 2 production. The optimal Pd 1 Ag 1 ‐NH 2 /C catalyst exhibits a high turnover frequency (TOF) of 6493.5 h −1 at 333 K based on the total amount of Pd, together with an H 2 selectivity of 100%. This study emphasizes the critical role of optimizing local transport pathways near catalytic centers chemically and further provides insights into the rational development of heterogeneous catalysts for FAD technologies.