Comparative study of organic removal by pre-adsorption oxidation and synchronous adsorption oxidation processes: Performance and mechanism.

Both adsorption and oxidation occur and contribute to organics removal in carbonaceous materials based advanced oxidation processes, while the correction of adsorption and oxidation, and the role of adsorption in the veritable removal of organic are not clear. Herein, we investigated the performance of carbamazepine (CBZ) removal by peroxymonosulfate (PMS) activated by magnetic Fe-doped biochar through two models of pre-adsorption oxidation and synchronous adsorption oxidation processes. The adsorption process was better fitted by pseudo-second-order kinetic model and the adsorption mechanism was obtained by comprehensive analysis of equilibrium adsorption capacities, surface functional groups, specific surface area, pore volume, and ID/IG value. It is noted that pre-adsorption highly inhibited the further oxidation of CBZ in 0.5Fe@LSBC700/PMS system due to the occupied catalytic active sites. Total CBZ removal in pre-adsorption oxidation (45 %) was inferior to synchronous adsorption oxidation (∼100 %), as well as the veritable CBZ oxidation removal of 27 % for pre-adsorption oxidation vs ∼100 % in synchronous adsorption oxidation at 30 min. Oxidation degradation of CBZ based on radical oxidation was identified by quenching experiments and electron paramagnetic resonance measurements. This work is conducive to identifying the role of adsorption during the removal of organics in the adsorption-oxidation process, as well as veritable adsorption and oxidation removal of organics.

Dispersed cobalt embedded nitrogen-rich carbon framework activates peroxymonosulfate for carbamazepine degradation: cobalt leaching restriction and mechanism investigation.

Metal leaching is a key issue in cobalt-based catalysts/PMS systems, which results in the decline of catalytic ability and serious secondary pollution. Hence, a nitrogen-rich carbon framework with cobalt node (Co-NC-920) with low cobalt leaching was synthesized based on zeolite imidazole framework (ZIF) and g-C3N4 to activate peroxymonosulfate (PMS) for the degradation of carbamazepine (CBZ). With the restriction of nitrogen-rich carbon framework, cobalt can disperse better and form stable cobalt-nitrogen bonds, thus only 0.09 mg/L cobalt ions were leached in the solution. More than 99.9% of CBZ can be removed within 30 min of PMS addition. Further investigation revealed that 1O2, SO4•- and high-valent cobalt species were primarily responsible for CBZ degradation in the Co-NC-920/PMS system and different reactive oxygen species (ROS) were distinguished and quantified, finding 1O2 was predominant. The degradation process was realized by the coexistence of free radicals and non-free radicals. Moreover, CBZ degradation capacity of the catalyst was evaluated under the influence of common anions and in actual waterbody. Finally, the possible degradation pathways of CBZ were proposed and the toxicity of the intermediates was analyzed. This work provides a new approach for the synthesis of cobalt-based nitrogen-rich carbon catalysts with low leaching and high efficient.