'Green-to-Green': Iron oxides embedded in lignin-based carbon scaffolds for water remediation via oxidation excluding free-radical pathways.

Abstract

Advanced oxidation processes (AOP) are a common tool to remove organic compounds from the water cycle. The process is mostly relied on free radicals (i.e., SO4•- and HO•) with high oxidation power in solution. Surface-mediated mechanism could improve this process to prevent undesired quenching of aqueous radicals that widely exists in free radical pathways and alleviate metal leaching through direct electron transfer. In this work, a facile low-temperature pre-treatment combined with pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin derived bio-char (γ-Fe2O3 @KC), upon which radicals stay surface mediated and the activity-stability trade-off is achieved for pollutant degradation. The γ-Fe2O3 @KC is capable of activating PMS to generate non-radical species which are more stable (1O2 and Fe(V)=O) and of enhancing electron transfer efficiency. A surface-bound reactive complex (Catalyst-PMS*) was identified by electrochemical characterization and was discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. We analyzed the γ-Fe2O3 @KC as a PMS-activating catalyst for a wider range of oxidation targets, such as Rhodamine B (∼100%), p-nitrophenol (∼85%), and Ciprofloxacin (∼63%), and found competitive removal efficiencies. The system also shows an encouraging reusability for at least 5 times and high stability at pH 3-9, and the low concentration of iron in γ-Fe2O3 @KC/PMS system implies the carbon scaffold of biochar alleviate the leakage process. The combined findings highlight the applicability in 'green (source) to green (application)' processes using cost-effective and bio-friendly iron@carbon catalysts, where alternative oxidation pathways are activated to play a dominant role for water purification.