Engineering the dynamic reactant-electrode interface in electroreduction systems: advances, challenges and prospects

Electrochemical reduction systems are pivotal for renewable energy conversion and sustainable chemical synthesis, yet their efficiency and selectivity are fundamentally governed by dynamic processes at the reactant-electrode interface. Moving beyond the traditional focus on static catalyst design, this review highlights the critical importance of actively engineering the dynamic interfacial microenvironment to control electroreduction pathways and modulate kinetics-related issues. At the beginning, we systematically examine the core interfacial determinants, including rate-limiting barriers, electronic structures, and adsorption-desorption balance, that dictate catalytic performance across key reactions. Central to this discussion is the dual modulation of interfacial electric fields and proton transfer dynamics. Electric field engineering strategies encompassing external electric bias, cation effects, geometric enhancement, and built-in electric fields are analysed for their ability to concentrate reactants, stabilize intermediates, and steer selectivity. Concurrently, proton transfer modulation centred on the proton-coupled electron transfer mechanism and facilitated by strategies such as controlling active hydrogen behaviour, employing Lewis acid-base pairs, and engineering the local pH, is explored to overcome kinetic bottlenecks and suppress competing side reactions. Furthermore, we highlight the transformative impact of advanced computational methods and machine learning in elucidating interfacial phenomena and accelerating the rational design of optimal interfaces. By integrating multiscale simulations with data-driven approaches, these tools bridge atomic-scale understanding with system-level performance. Collectively, this review provides a comprehensive framework for manipulating the dynamic electrode-reactant interface, offering strategic insights to enhance activity, selectivity, and stability in next-generation electroreduction systems for energy and environmental applications.