Iron containing sludge-derived carbon towards efficient peroxymonosulfate activation: Active site synergy,...

Converting industrial sludge into catalytic materials for water purification is a promising approach to simultaneously realize effective disposal of sludge and resource of water. However, manipulating the high efficiency remains a huge challenge due to the difficulty in the active sites control of the sludge. Herein, we proposed a constitutive modulation strategy by the combination of hydrothermal and pyrolysis (HTP) for the fabrication of defects-assistant Fe containing sludge-derived carbon catalysts on upgrading performance in peroxymonosulfate (PMS) activation for pollutant degradation. Adjustable defects on dyeing sludge-derived carbon catalysts (DSCC) were achieved by introducing oxygen or nitrogen functional precursors (hydroquinone or p-phenylenediamine) during hydrothermal processes and by further pyrolysis, where O was detrimental while N was beneficial to defect generation. Compared to the DSCC with less defects (DHSC-O), the defect-rich sample (DHSC-2N) exhibited superior catalytic performance of PMS activation for bisphenol A (BPA) elimination (k = 0.45 min^-1, 2.52 times of DHSC-O), as well as 81.4% total organic carbon (TOC) removal. Meanwhile, the degradation capacity was verified in wide pH range (2.1-8.1) and various aqueous matrices, reflecting the excellent adaptability and anti-interference performance. Furthermore, the continuous-flow experiments on industrial wastewater showed synchronous BPA and chemical oxygen demand (COD) removal, implying great potential for practical application. Solid electron paramagnetic resonance (EPR) and ⁵⁷Fe Mösssbauer spectra analysis indicated that the defects acted as secondary active sites for Fe sites, which were beneficial to accelerating the electron transfer process. The only Fe active sites preferred the radical pathway. The controllable reaction tendency provides possibilities for the on-demand design of sludge-based catalysts to meet the requirements of practical wastewater treatment under Fenton-like reaction.