Synergy of pore confinement and co-catalytic effects in Peroxymonosulfate activation for persistent and selective removal of contaminants

The activation of peroxymonosulfate (PMS) through nanoconfinement and co-catalytic effects has demonstrated considerable promise in environmental remediation. Nevertheless, the attainment of persistent efficiency and specificity for pollutant degradation remains a formidable obstacle. Herein, we proposed a solvent-free molten approach to convert a mixture of zeolitic imidazolate frameworks (ZIFs) and MoS₂ into 3D integrated cobalt-molybdenum bimetallic nitrogen-doped porous carbon foam with catalytic/co-catalytic performance (MC@NCF). The integrated materials exhibited exceptional efficiency in degrading contaminants based on the synergy of pore confinement and co-catalytic effects, achieving almost 100 % tetracycline degradation in 10 min with a k-value as high as 112.44 min⁻¹·M⁻¹, which was superior to the existing catalysts reported so far. The experimental findings revealed that the structural adjustment of MC@NCF significant accelerated the mass transfer through the formation of interfacial Mo-S/O-Co and Mo-N-Co/C bonds electron-tuning bridges between pore-confined micro-units, leading to the increased singlet oxygen (¹O₂) yield. Therefore, the MC@NCF exhibited more remarkable stability without interference from coexisting inorganic ions and cations, humic acid, and water matrices. Moreover, a flow-through nanoreactor was constructed and acquired efficient reactivity with negligible biotoxicity, and easy nanocatalyst recycling after continuous operation. The possible reactivity mechanism was identified by Frontier molecular orbital theory HOMO-LUMO, Fukui function, LC-MS, EPR, in-situ ATR-FTIR, and Raman analyses. Our results will guide integrated “catalytic/co-catalytic” nanoconfined MOF derivatives design to further enhance deep water purification technology.