Mechanisms of interaction between metal-organic framework-based material and persulfate in degradation of organic contaminants (OCs): Activation, reactive oxygen generation, conversion, and oxidation.

Metal-organic frameworks (MOFs)-based materials have been of great public interest in persulfate (PS)-based catalytic oxidation for wastewater purification, because of their excellent performance and selectiveness in organic contaminants (OCs) removal in complex water environments. The formation, fountainhead and reaction mechanism of reactive oxygen species (ROSs) in PS-based catalytic oxidation are crucial for understanding the principles of PS activation and the degradation mechanism of OCs. In the paper, we presented the quantitative structure-activity relationship (QSAR) of MOFs-based materials for PS activation, including the relationship of structure and removal efficiency, active sites and ROSs as well as OCs. In various MOFs-based materials, there are many factors will affect their performances. We discussed how various surface modification projects affected the characteristics of MOFs-based materials used in PS activation. Moreover, we revealed the process of ROSs generation by active sites and the oxidation of OCs by ROSs from the micro level. At the end of this review, we putted forward an outlook on the development trends and faced challenges of MOFs for PS-based catalytic oxidation. Generally, this review aims to clarify the formation mechanisms of ROSs via the active sites on the MOFs and the reaction mechanism between ROSs and OCs, which is helpful for reader to better understand the QSAR in various MOFs/PS systems.

pH adjustable MgAl@LDH-coated MOFs-derived Co2.25Mn0.75O4 for SMX degradation in PMS activated system.

Sulfate radical-based advanced oxidation processes (SR-AOPs) is considered as one of the most promising technologies for antibiotic pollution. In this study, a core-shell catalyst of cobalt-manganese oxide derived from CoMn-MOFs coating by MgAl-LDH (Co/Mn@LDH) was synthesized for peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX). Degradation efficiency of nearly 100% and a mineralization efficiency of 68.3% for SMX were achieved in Co/Mn@LDH/PMS system. Mn species and out shell MgAl-LDH greatly suppressed the cobalt ions leaching, which only 23 µg/L Co ions were detected by ICP after the reaction. SO4·- was identified as dominant reactive species in the system. Furthermore, the possible reactive sites of SMX were predicted by the density functional theory (DFT) calculations. And the intermediates of SMX were detected by LC-MS and the degradation pathway was proposed based on the results above. The ECOSAR results suggested the intermediates of SMX showed a relatively low toxicity compared to SMX, indicating huge potential of utilization of Co/Mn@LDH in SR-AOPs system.

Core-shell magnetic CFO@COF composites toward peroxymonosulfate activation for degradation of sulfamethoxazole from aqueous solution: A comparative study and mechanistic consideration.

A core-shell covalent organic framework encapsulated Co1.2Fe1.8O4 magnetic particles (CFO@COF) was designed and prepared successfully to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) degradation. It displays amazing catalytic reactivity since the unique interior structure and synergistic effect between COF shell and CFO core, reaching 99.8% removal of SMX (10 mg/L) within 30 min and 90.8% TOC removal. The synergy between bimetals vests high reactivity to CFO core. And the outer COF shell can stabilize the CFO core under intricate reaction conditions to restrain the leaching of Co ions (decreased from 0.75 to 0.25 mg/L). Further investigation compared the activation mechanism in two different system, CFO/PMS system and CFO@COF/PMS system. The result showed that the radical mechanism controlled by SO4⋅- guided the SMX degradation in CFO/PMS system whereas the 1O2 played a pivotal role in CFO@COF/PMS system called non-radical leading. The influences of various factors on degradation experiments and SMX degradation pathway were also studied. Most importantly, risk assessment in CFO@COF/PMS/SMX system was estimated via "ecological structure activity relationships". In most case, the toxicities of intermediates were lower than the initial samples, which confirmed the effectiveness of CFO@COF/PMS/SMX system in the reduction of toxicity of SMX.