Synthesis of stabilized zero-valent iron particles and role investigation of humic acid-Fe^x+ shell in Fenton-like reactions and surface stability control

Herein, a novel humic acid-Fex+ complex-coated ZVI (HA-Fex+@ZVI) was synthesized and used to activate peroxydisulfate (PDS) for phenol degradation. The HA-Fex+ shell selectively reacted with PDS rather than O-2, leading to the formation of modified ZVI with excellent surface stability in storage and ultraefficient PDS activation in advanced oxidation processes (AOPs). As a result, the phenol degradation and PDS activation efficiencies of HA-Fex+@ZVI/PDS were similar to 14.4 and similar to 1.8 times higher than those of ZVI/PDS, respectively. Mechanistic explorations revealed that the replacement of the HA-Fex+ shell relative to the original passivation layer of ZVI greatly changed the SO4 center dot- generation pathway from a heterogeneous process to a homogeneous process, resulting from the slow exposure of Fe-0 (generating dissolved Fe2+) and the depolymerized HA (enhancing the Fe3+/Fe2+ cycle). Based on experimental analysis and density functional theory (DFT) calculations, the Fe3+ in HA-Fex+ could be reduced to Fe2+ by PDS, resulting in the disintegration of the HA-Fex+ shell and exposure of Fe-0 core active sites. Furthermore, compared to similar catalysts synthesized with commercial HA and traditional chemicals, HA-Fex+@ZVI synthesized with multiple waste biomasses exhibited better performance. This research provides valuable insights for designing ZVI-based catalysts with excellent storage stability and ultraefficient PDS catalytic activity for AOPs.