Tailoring reactivity in MOF derivatives via thermally induced amorphization: Synergistic crystalline/amorphous heterointerfaces for efficient 4-nitrophenol detoxification

The development of electrocatalysts capable of efficient detoxification of nitroaromatic contaminants via selective nitro-group reduction into valuable amino derivatives with high efficiency is gaining increasing interest in both chemical valorization and environmental remediation. Herein, we present an incompletely pyrolyzed bimetallic electrocatalyst with structurally ambiguous low-crystallinity domains, where irregular interconnections of primary nuclei achieved through phase-transition-proximal pyrolysis enable effective electrochemical hydrogenation of 4-nitrophenol (4-NP). Experimental validation results demonstrate that precisely controlled pyrolysis preserves the structural integrity of the pristine framework while generating abundant accessible catalytically-active sites, synergistically boosting hydrogenation efficiency. Further, systematic DFT calculations were conducted to decipher the intrinsic mechanism of the electrocatalytic activity enhancement by crystalline/amorphous heterointerfaces. Through precision-controlled thermal amorphization, this work establishes a dual-functional electrocatalyst design approach that concurrently achieves selective biomass valorization and detoxification of persistent organic pollutants.