Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single‐Atom Catalysts throughp‐nJunction Rectification

Abstract Fine‐tuning single‐atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploit p ‐type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeN x ) and rectify their local charge density by an n ‐type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing an n ‐type gallium monosulfide that features a low work function generates a space‐charged region across the junction interface, and causes distortion of the FeN 4 moiety and spin‐state transition in the Fe II center. This catalyst shows an over two‐fold higher specific oxygen‐reduction activity than that of pristine FePc. We further employ three other n ‐type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN 4 and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.