In Situ Tailored Frustrated Lewis Pairs on Asymmetric Bi─Ov─In Motifs Domino‐Direct High‐Efficiency Urea Electrosynthesis

Abstract The green urea synthesis via co‐electrolysis of waste nitrate and CO 2 is alluring but challenging, especially with insufficient selectivity caused by thermodynamic differences and kinetic mismatch between multi‐step conversion processes. Here, a domino effect‐oriented electrosynthesis strategy is showcased to steer cascade reactions in upgrading nitrate and CO 2 toward urea of high selectivity on Bi‐doped In 2 O 3 with asymmetric oxygen vacancies (O v ). The conventionally arbitrary reaction mode can be vectored and re‐customized by stable and cumulative * NH 2 intermediates in situ derived from priority nitrate reduction reaction, which not only form surface frustrated Lewis pairs (SFLPs, Bi─O v ─In─NH 2 ) with Bi Lewis acid sites to synergistically adsorb and activate CO 2 but also provide more opportunities for sluggish C─N coupling, delivering an unprecedented urea Faradic efficiency of 80.2% and an impressive urea yield of 2.38 × 10 3 µg h −1 mg cat. −1 at −0.4 V versus RHE. The atomically dispersed Bi sites promote the protonation of * NO to form nucleophilic * NH 2 intermediates, which can be stabilized in the electrophilic region mediated by asymmetric O v , permitting two nucleophilic attacks to complete the C─N coupling. The domino modeling protocol via positioning a specific intermediate in situ tailors the parallel conversion process and may guide selectivity control of electrosynthesis.