Computational Approaches for Designing Heterostructured Electrocatalysts

Electrocatalysts for oxidation and reduction reactions are crucial for sustainable energy production and carbon reduction. While precious metal catalysts exhibit superior activity, reducing reliance on them is necessary for large‐scale applications. To address this, transition metal‐based catalysts are studied with strategies to enhance catalytic performance. One promising strategy is heterostructures, which integrate multiple materials to harness synergistic effects. Developing efficient heterostructured electrocatalysts requires understanding their intricate characteristics, which poses challenges. While in situ and operando spectroscopy provides insights, computational materials science is essential for capturing reaction mechanisms, analyzing the origins at the atomic scale, and efficiently exploring innovative heterostructures. Despite growing recognition of computational materials science, standardized criteria for these systems remain lacking. This review consolidates case studies to propose approaches for modeling and analyzing heterostructures. It categorizes heterostructure types into vertical, semivertical, and lateral, defines their characteristics, and propose insights into minimizing or exploiting strain effects from lattice mismatches. Furthermore, it summarizes computational analyses of heterostructure stability and activity across reactions, including oxygen evolution, hydrogen evolution, oxygen reduction, carbon dioxide reduction, nitrogen reduction, and urea oxidation. This review provides an overview to refine heterostructure designs and establish a framework for systematic modeling and analysis to develop efficient electrocatalysts.