Regulating the Local Coordination of Cd‐Glutamate Through Ligand Chirality for Efficient Alkaline Hydrogen Evolution

Abstract

ABSTRACT The rational regulation of local coordination environments in metal‐organic complexes provides an effective strategy for tuning electrocatalytic activity; however, the influence of ligand chirality on hydrogen evolution remains largely unexplored. Herein, we report a series of optically active Cd‐glutamate coordination complexes synthesized from D‐, L‐, and racemic DL‐glutamate ligands and systematically investigate how ligand stereochemistry governs their structural organization and alkaline hydrogen evolution reaction (HER) performance. Density functional theory (DFT) identifies an oxygen‐coordinated Cd‐glutamate configuration as the thermodynamically preferred structure, while comprehensive characterization supports that ligand chirality subtly modulates the local coordination symmetry, morphology, and electronic environment without altering the Cd 2+ oxidation state. Electrochemical measurements reveal that the D‐derived complex exhibits the highest HER activity compared to the L and DL counterparts, delivering a low overpotential of 188 mV at 10 mA cm −2 with a Tafel slope of 148 mV dec −1 , together with the lowest charge‐transfer resistance and excellent long‐term electrochemical stability. Comparative DFT calculations further indicate that ligand chirality and the HOMO–LUMO gap alone do not directly account for the enhanced HER activity of D1, suggesting that its superior performance arises from the combined effects of chirality‐dependent local coordination, structural organization, morphology, and interfacial properties.