Engineering heterostructures for electrocatalysis and energy storage: classification, design, computational insights and property modulation

Heterostructure engineering involves strategic integration of two or more chemically or structurally distinct materials with well-defined interfaces gained considerable attention owing to its capacity to induce synergistic effects thar are absent in individual constituents. Heterostructure allow deliberate tuning of intrinsic electronic structures, band alignments and interfacial charge redistribution enable superior performance in both energy storage and electrocatalytic activity. Recent advancement in heterostructure demonstrate diverse architectures that enhance the availability of electrochemical active site, accelerate ion diffusion, reduce overpotentials, and improve electrochemical stability. Complementary computational methods such as Density Functional theory (DFT), Molecular Dynamics (MD), and Machine learning (ML), have further deepened understanding of charge transfer mechanisms, built-in electric fields, and diffusion kinetics at heterointerfaces, thereby accelerating the rational design of heterostructure materials. This review provide comprehensive overview of structural, electronic, and electrochemical characteristics of heterostructure, critically examines their synthesis strategies, and highlight their role in advancing EWS and SC technologies.