Mineralization versus polymerization pathways in heterogeneous Fenton-like reactions

Fenton reaction has been widespread application in water purification due to the excellent oxidation performances. However, the poor cycle efficiency of Fe(III)/Fe(II) is one of the biggest bottlenecks. In this study, graphite (GP) was used as a green carbon catalyst to accelerate Fenton-like (H₂O₂/Fe³⁺ and persulfate/Fe³⁺) reactions by promoting ferric ion reduction and intensifying diverse peroxide activation pathways. Significantly, the carboxyl group on GP anchors iron ions to form GP-COOFe(III) which promote persulfate adsorption to form surface complexes and induce an electron transfer pathway (ETP). While the electron-rich hydroxyl and carbonyl groups will combine to from GP-COFe(II), a reductive intermediate to activate peroxide to generate free radicals (from H₂O₂ and PDS) or high-value iron [Fe(IV)] (from PMS). Consequently, different pathways lead to distinct degree of oxidation: i) radicals in H₂O₂/Fe³⁺/GP prefer to mineralize bisphenol A (BPA) with no selectivity; ii) Fe(IV) in PMS/Fe³⁺/GP partially oxidizes BPA but cannot open the aromatic ring; iii) ETP in PMS/ or PDS/Fe³⁺/GP drives coupling reactions to form polymeric products covered on catalyst surface. Thus, rational engineering surface functionality of graphite and selecting proper peroxides can realize on-demand selectivity and oxidation capacity in Fenton-like systems.