Minimizing H ₂ O ₂ Loss in Industrial Electrosynthesis via Asymmetric Main‐Group Sn Single‐Atom Catalysts

Abstract The electrosynthesis of hydrogen peroxide (H 2 O 2 ) via the two‐electron oxygen reduction reaction offers an appealing and sustainable route for on‐site H 2 O 2 production. However, its broader applicability is constrained by subpar yields, primarily resulting from insufficient selectivity and the occurrence of electrochemical and/or chemical decomposition of H 2 O 2 . Herein, we demonstrate that asymmetric N/S co‐coordinated main‐group Sn sites can effectively stabilize oxygen intermediates and rapidly desorb the generated H 2 O 2 , thereby enhancing 2e − ORR pathway selectivity while suppressing undesirable H 2 O 2 decomposition reactions. At an industrially relevant current density of 300 mA cm −2 , the main‐group catalyst achieves an exceptional H 2 O 2 faradaic efficiency of 93%. When scaled to an industrial sized area of 100 cm 2 , the pilot reactor delivers an impressive H 2 O 2 production rate of 353.5 mmol h −1 at 20 A. In situ characterizations and theoretical simulations reveal that the main‐group Sn sites exhibit inertness toward activation of H 2 O 2 , thereby mitigating H 2 O 2 loss in electrosynthesis. The asymmetric N/S‐coordination enhances electron transfer between the Sn center and oxygen intermediates, stabilizing the *OOH intermediate and facilitating H 2 O 2 generation. This work presents a promising strategy for minimizing H 2 O 2 loss in electrochemical production via the rational design of main‐group catalysts with well‐defined coordination and electronic structures.