The relationship between electronic behavior of single atom catalysts and CO2 reduction to oxygenates

Single-atom catalysts (SACs), with 100% atomic efficiency and distinctive electronic properties, show excellent catalytic performance for CO₂ reduction to oxygenates. However, the electronic structure of active sites and key intermediates undergo continuous changes during the reaction on SACs. It is challenging to explain these phenomena through structure-activity relationship. Herein, the “electronic behavior” elucidates the dynamic nature of electronic interactions between active sites and key intermediates. In this review, we invesitgate the transformation of the electronic structure within the CO₂ molecule and the active site of SACs during CO₂ activation, elucidating the complex interplay between these two entities. Then, we delve into the electronic change processes involved in thermal, electro-, and photo-catalytic CO₂ conversion, providing in-depth discussions. Additionally, the influence of the catalyst's electronic behavior on the structure-activity relationship is delineated with precision. At last, the challenges and future perspectives of electronic behavior for SACs are outlined.