Engineering chirality at electrochemical interfaces: design principles, mechanisms, and applications

Electrochemical sensing provides a rapid and sensitive route for enantiomer discrimination but remains limited by the challenge of converting subtle stereochemical differences into reliable analytical signals. Recent advances demonstrate that this limitation can be addressed through rational design of the electrode interface, where chiral recognition and charge transport are co-optimized within engineered materials. This review examines how carbon nanostructures, metal and metal oxide nanomaterials, polymers, and metal–organic frameworks are integrated with molecular and supramolecular chiral elements to produce synergistic sensing interfaces. Enantioselectivity is shown to arise from differential stabilization of diastereomeric interactions governed by coordination chemistry, hydrogen bonding, and host–guest inclusion, coupled with efficient electron-transfer pathways. Emerging approaches based on intrinsically chiral materials, stochastic sensing, and photoelectrochemical transduction further expand the scope of electrochemical enantioanalysis. By correlating material architecture with sensing performance, this review defines key design principles for achieving high sensitivity, selectivity, and robustness, and outlines strategies for advancing electrochemical chiral sensing toward practical applications in complex analytical environments.