Dual redox cycles of Mn(Ⅱ)/Mn(III) and Mn(III)/Mn(IV) on porous Mn/N co-doped biochar surfaces for promoting peroxymonosulfate activation and ciprofloxacin degradation

Abstract

Mn and N co-doped biochar (Mn-N-TS) was prepared as an effective catalyst to activate peroxymonosulfate (PMS) for ciprofloxacin (CIP) degradation. As opposed to Mn-TS and N-TS, Mn-N-TS had more active sites containing N and Mn, as well as a greater specific surface area (923.733 m2 g−1). The Mn-N-TS exhibited excellent PMS activation ability. In the Mn-N-TS/PMS system, the CIP removal efficiency was 91.9% in 120 min. Mn and N co-doping could accelerate electron transfer between CIP and PMS molecules. Simultaneously, defect sites, graphitic N, pyridinic N, C═O groups, and Mn(II)/Mn(III)/Mn(IV) redox cycles acted as active sites to activate PMS and generate free radicals (OH, SO4− and 1O2). Furthermore, the Mn-N-TS/PMS system could effectively degrade CIP in a wide pH range, background substances, and actual water. Finally, a probable mechanism of PMS activation by Mn-N-TS was proposed. In conclusion, this work gave a novel direction for the rational design of Mn and N co-doped biochar.