Beyond traditional electrocatalysts: polyoxometalates at the frontier

Intensified global energy demand and environmental concerns have made sustainable energy generation a global necessity. Water electrolysis and other processes, such as the CO₂ reduction reaction (CO₂RR) and nitrogen reduction reaction (NRR), are key green energy pathways that require efficient electrocatalysts with stability, multifunctionality, and structural diversity. Polyoxometalates (POMs) are exceptional due to their compositional diversity, structural versatility, active sites, and tunable electronic properties. However, challenges such as leaching, agglomeration, and low stability persist. In this frontier article, we focus on the exploration of POM-based and POM-derived materials for promising applications as electrocatalysts. We discuss advances in the POM materials (hybrids/derivatives) for electrocatalysis, with an emphasis on synthesis strategies, nanostructure design, and property enhancement through element doping, electronic modulation, heterojunction construction, morphological control, surface/interface engineering, and theoretical studies. We aim to summarize the current state of the art, highlight emerging trends, and provide insights into the future directions of POM electrocatalyst research to drive innovation in sustainable energy technologies.