Breaking Scaling Relations to Achieve an Electrochemical Potential Window Strategy for Highly Selective Urea Electrosynthesis From N 2 and CO 2

ABSTRACT Electrochemical co‐reduction of nitrogen (N 2 ) and carbon dioxide (CO 2 ) under ambient conditions offers a sustainable route for urea synthesis, while this desirable pathway suffers from selectivity challenge because of an inferior competition with numerous parallel reactions. Available strategy to selectively boost urea electrosynthesis and suppress the competitive reactions is absent, because they share the same intermediates which are limited by the well‐established scaling relations. Herein, we design a multi‐site NbCo 3 intermetallic compound, which imposes a dynamic strain effect on intermediates to break the scaling relations, achieving to gather radical intermediates to participate in C−N coupling while preventing their further protonation. Based on constant potential density functional theory (CP‐DFT) computations, an electrochemical potential window is evolved that NbCo 3 (001) obtains a prior selectivity toward urea electrosynthesis when the electrode potential is below −0.25 V versus the reversible hydrogen electrode (RHE). This work provides an available strategy to improve the catalytic selectivity of urea electrosynthesis, which accelerates the development of highly efficient catalysts.