Carbon Vacancy Manipulating the Microenvironment of Pd Clusters for Gram‐Scale Ammonia Production and Efficient Zn‐Nitrate Batteries

ABSTRACT Emerging flexible carbon nanofiber (CNF) membranes, are widely used due to its advantages of adhesive free operation, inherent flexibility, structural stability, and low cost. However, most studies focused on CNF membranes as supports, neglecting inherent carbon defects. Herein, a carbon vacancy modified palladium‐doped CNF (Pd‐CNF) is synthesized via electrospinning and electrodeposition. Due to the synergistic effect of carbon vacancies and Pd clusters, the ammonia production rate of Pd‐CNF catalyst is 180 mg h −1 mg cat −1 , the Faraday efficiency (FE) is 95%, and it can operate stably for more than 1100 h. Pd clusters facilitate nitrate adsorption and hydrogenation, while carbon vacancies anchor Pd clusters and modulate the electronic structure of catalytic sites. The catalyst demonstrates robust stability and adaptability across diverse industrial wastewaters rich in nitrate, enabling gram‐scale ammonia production. As a cathode material in Zn‐nitrate batteries, Pd‐CNF possesses a high NH 3 yield (0.42 ± 0.05 mmol h −1 cm −2 ) and FE value (86% ± 5%). This work re‐examines the role played by inherent carbon defects in CNF membranes for anchoring and regulating metal clusters, achieving gram‐scale ammonia synthesis and efficient Zn‐nitrate batteries.