Oxygen evolution reaction (OER) is a critical process in renewable energy technologies. However, its large-scale application faces two major challenges: slow reaction kinetics and heavy reliance on noble metal catalysts. Tricobalt tetraoxide (Co₃O₄) is an affordable transition metal oxide with a favorable electronic structure, emerges as a promising alternative to noble metals. However, its performance is constrained by linear scaling relationship (LSR). LSR refer to the linear correlations between the adsorption free energies of intermediates, which prevent the simultaneous optimization of all steps, thereby limiting the maximum catalytic performance. Due to these scaling relationships, Co₃O₄-based catalysts following the conventional adsorbate evolution mechanism (AEM) inevitably require a high overpotential. To overcome this limitation, researchers have developed various strategies to modulate OER pathway. These methods not only optimized AEM but also promote a shift toward other mechanisms, such as lattice oxygen mechanism (LOM) or oxide path mechanism (OPM). This review systematically classifies different strategies for modifying Co₃O₄-based catalysts. It focuses on these strategies can not only improve but also completely change the OER reaction pathway, thus providing a clear design guide to overcome the scaling relationship and direct future development.

Electrochemical reduction of CO₂ (ECO₂RR) into value-added fuels and chemicals presents a promising avenue for mitigating CO₂ emissions while simultaneously contributing to economic growth, thereby addressing critical environmental and energy challenges. However, the large-scale implementation of ECO₂RR is significantly impeded by the necessity to design efficient catalysts that exhibit both high activity and selectivity. These catalysts must overcome the sluggish kinetics associated with ECO₂RR as well as the competing hydrogen evolution reaction. In recent decades, electrospun nanofibers have garnered considerable attention as potential catalysts for ECO₂RR, attributable to their high surface area with abundant active sites, tunable functionalities, and enhanced selectivity. This review comprehensively examines the rational design of ECO₂RR catalysts utilizing electrospinning technology. We commence with an in-depth exploration of the principles underlying the electrospinning process and subsequently summarize key factors influencing this process, including solution parameters, environmental conditions, and electrospinning operational parameters. Moreover, we discuss recent advancements in ECO₂RR catalysts synthesized through electrospinning, encompassing carbon nanofibers, composite nanofibers, and metal nanofibers. Finally, we delineate future perspectives and the challenges that electrospun materials face in the context of ECO₂RR applications. This review aims to inspire high-quality research directed toward the advancement of electrospun materials for improved performance in ECO₂RR.