Probing Electrocatalyst Design for Product Selectivity in CO ₂ Reduction

ABSTRACT Electrochemical CO 2 mitigation offers a transformative route to sustainability, offering a powerful solution to the twin challenges of rising global energy demand and climate change. The formation of multicarbon products, particularly hydrocarbons and oxygenates, is of considerable industrial significance owing to their higher energy density and value as key chemical feedstocks. Despite significant progress, pivotal challenges persist in optimizing selectivity, streamlining reaction pathways, and enabling scalable implementation. This review outlines recent progress in the rational design of electrocatalysts for the selective CO 2 reduction reaction (CO 2 RR), emphasizing operational conditions and strategies that manipulate the local reaction microenvironment to steer selectivity and efficiency. It presents an in‐depth discussion of the stability of Cu‐ and non‐Cu‐based electrocatalysts, including single‐atom and molecular catalysts, and their degradation mechanisms, with both ex/in situ analysis and computational insights. Special attention is given to structure‐performance relationships and dynamic surface reconstructions under reaction conditions. Finally, it sheds light on promising pathways for achieving highly selective formation of higher‐order hydrocarbons (C 3 −C 6+ ). The review concludes by identifying pressing challenges and highlighting emerging frontiers in CO 2 RR that are poised to accelerate progress. These insights collectively chart a course for translating CO 2 R research into viable industrial applications, thereby advancing global efforts toward carbon neutrality.