Spin effects in electrocatalysis: underlying mechanisms and reactivity regulation

The pursuit of sustainable energy conversion technologies has positioned electrocatalysis at the forefront of modern research, yet the efficiency of key electrochemical reactions remains constrained by fundamental limitations in reaction kinetics and thermodynamics. Recent breakthroughs have established electron spin control as a transformative paradigm, achieved through the modulation of intrinsic catalyst properties (e.g., doping, strain, interface engineering) and external field induction (e.g., magnetic fields). These approaches primarily enhance catalytic performance by regulating the electronic structure of active centers, facilitating charge transport, and optimizing reaction pathways. This review systematically outlines the fundamental principles of spin-dependent processes in electrocatalysis, with a focus on three core mechanisms: (i) modulating the electronic structure and adsorption thermodynamics of active centers through super-exchange (SE), double-exchange (DE), and spin-orbit coupling (SOC); (ii) facilitating charge carrier separation and transport kinetics via spin polarization and DE-mediated quantum spin-exchange interactions; and (iii) steering reaction pathways and product selectivity through chirality-induced spin selectivity (CISS), SOC, and spin-polarized charge injection. The underlying mechanisms linking electron spin to enhanced electrocatalytic activities are discussed in detail. Finally, this review concludes with a summary and future perspectives on spin-mediated electrocatalysis, aiming to provide a comprehensive understanding of spin effects and their regulation for improved electrocatalytic applications.