Electrocatalysis and Photoelectrocatalysis: Perspective from Physicochemical Mechanisms to Applications

Abstract Electrocatalytic and photoelectrocatalytic technologies, which enable the direct conversion of renewable electricity and solar energy into storable and high-value chemicals, have emerged as key research frontiers in addressing the global energy crisis and environmental challenges. This review aims to systematically elucidate recent advances in the field, insights from fundamental physical mechanisms to practical applications. First, we provide an in-depth analysis of the core physicochemical principles governing catalytic processes, including electronic structure, band engineering, interfacial charge transfer kinetics, and key reaction pathways. Second, we highlight the advanced characterization techniques for probing the dynamic behavior of catalysts, such as in situ electron microscopy, X-ray absorption spectroscopy, and vibrational spectroscopy. These “eyes” offer compelling evidence for unveiling the nature of active sites and their dynamic reconstruction processes. Based on these foundational concepts, this review further showcases the applications of rationally designed catalytic materials across multiple fields: clean energy synthesis, carbon and nitrogen resource recycling and conversion, deep purification of environmental pollutants, green chemical synthesis, as well as biosensing and environmental monitoring. Finally, we preconceive a new paradigm of “intelligent catalysis research and development”, which integrates high-throughput computation, artificial intelligence, and automated experimentation. We also emphasize that advancing multiscale theoretical simulations, in situ characterization of complex systems, and system-level integration and optimization are critical steps toward practical implementation. This work not only offers a solid theoretical framework and methodology for deepening the understanding of electrocatalytic and photoelectrocatalytic processes but also outlines a roadmap for the design of next-generation intelligent catalytic systems toward sustainable development.