Fundamentals and Perspectives of Positively Charged Single-Metal Site Catalysts for CO2 Electroreduction

Single-atom catalysts (SACs) show superior efficiency in electrocatalytic carbon dioxide reduction, a key stage in achieving carbon neutrality. Atomically dispersed single-metal sites of SACs are invariably in a positive valence state; namely, they are positively charged single-metal sites (PCSSs). The PCSS catalysts generally possess a distinctive and asymmetric electronic structure, which enables the activation of linear carbon dioxide molecules and stabilizes miscellaneous intermediates during electrocatalysis. Herein, this review summarizes the manner in which the coordination environment, neighboring atoms or groups, and the interaction with the substrate modulate the distinctive electronic properties of PCSSs. Additionally, we overview the recently reported theoretical and experimental advances in terms of structure–performance relationship. Furthermore, we emphasize the previously underappreciated durability of positively charged single-metal sites in CO₂ reduction. Finally, we discuss several pending issues and potential breakthroughs of PCSSs for CO₂ reduction.