X-ray absorption spectroscopy and in situ electron paramagnetic resonance evidence were provided for the reduction of Cu(II) to Cu(I) species by alkynes in the presence of tetramethylethylenediamine (TMEDA), in which TMEDA plays dual roles as both ligand and base. The structures of the starting Cu(II) species and the obtained Cu(I) species were determined as (TMEDA)CuCl2 and [(TMEDA)CuCl]2 dimer, respectively.

Many reagents as electron sacrificers have been recently investigated to induce decomposition of permanganate (KMnO 4 ) to produce highly reactive intermediate Mn species toward oxidation of organic contaminants; however, this strategy meanwhile causes low KMnO 4 utilization efficiency. This study surprisingly found that graphite can mediate direct electron transfer from organics (e.g., sulfamethoxazole (SMX)) to KMnO 4 , resulting in high KMnO 4 utilization efficiency, rather than reductive sites of graphite-induced conversion of KMnO 4 to highly reactive intermediate Mn species. The galvanic oxidation process (GOP) and comparative experiments of different organic contaminants prove that the KMnO 4 /graphite system mainly extracts electrons from organic contaminants via a one-electron pathway instead of a two-electron pathway. More importantly, the KMnO 4 /graphite system has superior reusability, graphite can keep a long-lasting reactivity, and the KMnO 4 utilization efficiency elevates significantly after each cycle of graphite. The transformation of SMX in the KMnO 4 /graphite system mainly includes self-coupling, hydroxylation, oxidation, and hydrolytic reaction. The work will improve insights into the electrontransfer mechanism and unveil the advantages of efficient KMnO 4 utilization in the KMnO 4 -based technologies in environmental remediation.

No abstract

No abstract

No abstract