Main‐Group s‐Block Element Lithium Atoms within Carbon Frameworks as High‐Active Sites for Electrocatalytic Reduction Reactions

Abstract Inspired by the d ‐band center theory, previous studies mainly focus on transition metals as electrocatalytic active sites. The s ‐block metals in the periodic table, especially group ΙA metals with fewer valence electrons, are rarely reported as high‐activity electrocatalysts for reduction reactions due to the difficulties associated with their electronic structure regulation. Herein, theoretical calculations demonstrate that group ΙA element lithium (Li) embedded in N, O‐doped graphene is an effective electrocatalytic active center for carbon dioxide reduction reaction (CO 2 RR) and oxygen reduction reaction (ORR). This catalytic feasibility results from the s – p orbital hybridization between originally empty 2 p orbital of Li and the orbitals of coordinated atoms. This vacant 2 p orbital can serve as a site for additional p –π conjugation between Li and N, O‐doped graphene. Theoretically, the zigzag‐type Li–O 2 model shows remarkable CO 2 RR activity, while Li–pyridinic–N 1 ‐C 1 exhibits high ORR activity. Furthermore, a carbon‐based catalyst with well‐anchored Li atoms coordinated to N, O substituents is experimentally demonstrated to exhibit exceptional CO 2 RR activity (FE CO = 98.8% at −0.55 V) and ORR performance in acidic media ( E 1/2 = 0.77 V). This is the first report on bifunctional high‐performance electrocatalyst utilizing a group ΙA element with performance comparable to that of most previously reported transition‐metal‐based catalysts.