d‐Orbital Reconstruction in Pd‐Fe Metallene Aerogels Enables pH‐Universal Electrocatalysis of Acetonitrile to Ethylamine

ABSTRACT Orbital reconstruction plays a crucial role in modulating electrocatalytic performance by regulating intermediate adsorption, yet its application in acetonitrile reduction reaction (ARR) remains unexplored. Herein, for the first time, we develop PdFe metallene aerogels (MAs) as efficient catalysts for the pH‐universal electrosynthesis of acetonitrile to ethylamine. Notably, in membrane electrode assembly (MEA) system, PdFe MAs achieve ethylamine selectivity (89.34%), yield rate (7659.93 mmol h −1 g −1 Pd+Fe ), and Faradaic efficiency (FE) (70.98%) under acidic condition. Remarkably, both the FE and selectivity of PdFe MAs remain stable without any apparent degradation during 1000 h at 250 mA cm −2 . In neutral and alkaline electrolytes, PdFe MAs retain approximately 95% selectivity and FE, maintaining stable operation for 645 and 573 h at 250 mA cm −2 . The resulting Zn‐acetonitrile battery achieves a power density of 49.98 mW cm −2 and an open‐circuit voltage of 2.25 V, continuously powering a fan for 89 min. Mechanism studies reveal that Fe‐Pd d‐orbital coupling induces orbital reconstruction, which downshifts the Pd d‐band center to simultaneously optimize * H coverage and weaken intermediate adsorption. Coupled with the high specific surface area and efficient mass transport of MAs, this synergy enables outstanding pH‐universal ARR performance, offering a general design principle for sustainable electrosynthesis.