Recent Advancements in Electrocatalytic CO 2 Reduction Using Different Porphynoids

ABSTRACT The growing global energy demand and rapid growth in industrialization and urbanization have intensified the consumption of fossil fuels, leading to an alarming accumulation of CO 2 in the atmosphere. The rise in greenhouse gases contributes to severe environmental and health challenges. The reduction of CO 2 into energy dense products such as CO, formate, alcohols, and hydrocarbons offers a promising strategy to reduce these effects. The electrochemical CO 2 reduction (CO 2 RR) stands out among various approaches due to its compatibility with renewable electricity. However, activating the thermodynamically stable CO 2 molecule remains a significant challenge, and it requires the development of selective, robust, and efficient electrocatalysts. The N 4 ‐macrocyclic complexes, capable of mimicking enzymatic active sites and facilitating multi‐electron CO 2 transformations including porphyrins, corroles, and phthalocyanines (Pcs), have emerged as a distinct class of molecular catalysts. This review provides a comprehensive summary of recent progress in N 4 ‐macrocyclic metal complexes for CO 2 RR, focusing on their design principles, electronic structure modulation, and mechanistic insights.