Nanoporous Zero-Valent Transition Metals for Enhanced Peroxymonosulfate Activation toward Phenolic Pollutants...

This study reports a series of nanoporous Zero-valent metals (ZVMs) with bicontinuous ligament-channel structures and demonstrates their application in activating peroxymonosulfate (PMS) for the degradation of phenolic pollutants. Among them, zero-valent cobalt (ZVCo) exhibits exceptional PMS activation performance, achieving complete degradation of bisphenol A (BPA) and phenol within 4 and 8 min, respectively, surpassing most reported Co-based catalysts, which is attributed to the highly reactive metallic Co⁰ sites and the high Co²⁺/Co³⁺ ratio. ZVCo maintains rapid PMS activation across a broad pH range (3-11) and in real water matrices containing various inorganic ions, demonstrating strong practical application potential. By combining experimental techniques, in situ Raman spectroscopy, and density functional theory (DFT) calculations, the activation process of PMS on the ZVMs surface (including reaction free energies, electron density changes, bond length evolution, etc.), radical (SO₄ ^•- and •OH) and non-radical (¹O₂) pathways, along with the BPA degradation process, were systematically elucidated. Theoretical calculations established a volcano relationship between the adsorption energy of PMS on various surfaces of ZVMs and ΔG_OH*/ΔG_H*, providing theoretical insights into understanding the PMS activation efficiency of different ZVMs. This work offers atomic-level insights into the PMS activation mechanisms of ZVMs and provides valuable guidance for designing high-performance catalysts for pollutant degradation.