Removal of acetaminophen through direct electron transfer by reactive Mn₂O₃: Efficiency, mechanism and pathway

Mn₂O₃ with certain oxidative reactivity, was fabricated via sol-gel method and applied for the removal of acetaminophen (APAP). The mechanism of APAP oxidation was revealed in depth through electrochemical tests and X-ray photoelectron spectroscopy (XPS). Moreover, the selective abatement of various organic contaminants contained different functional groups by Mn₂O₃ was investigated through linear free energy relationship (LFER) estimated with peak potentials (E_op) of these organic contaminants. Under acidic condition, APAP could be effectively eliminated by Mn₂O₃. The open circuit potential (OCP) and zeta potential tests illustrate that the oxidative reactivity of Mn₂O₃ is associated to the surface acid-base behavior of Mn₂O₃ and its surface charge situation. The XPS experiments and Mn leaching results imply that Mn(III) could capture electron from APAP and release Mn²⁺ to aqueous phase. The intermediates could be ascribed to fragmentation of acetamido radicals and phenoxy radicals, both of which were formed through electron transfer from APAP to Mn₂O₃. The reactive Mn₂O₃ shows selective oxidation of different contaminants in the electron transfer process. LFER analysis indicates good negative linear correlation between lnk₁ and E_op of various pollutants. The efficiency of Mn₂O₃ in the elimination of APAP and selective oxidation of different contaminants suggest some new insights for transformation of APAP and other electron-rich pollutants in the environments.