Pyrolysis temperature-switchable Fe-N sites in pharmaceutical sludge biochar toward peroxymonosulfate activation for efficient pollutants degradation

Abstract

Pyrolysis of pharmaceutical sludge (PS) is a promising way of safe disposal and to recover energy and resources from waste. The resulting PS biochar (PSBC) is often used as adsorbent, but has seldom been explored as catalyst. Herein we demonstrate that PSBC (0.4 g/L) could efficiently activate peroxymonosulfate (PMS) to 100% degrade 4-chlorophenol (4-CP) with rate constants of 0.42-1.70 min^-1, outperforming other reported catalysts. Interestingly, the PMS activation pathway highly depended on PSBC pyrolysis temperature, which produced dominantly high-valent iron species (e.g., Fe^IVO²⁺) at low temperature but more sulfate radical (SO₄^·-) and hydroxyl radical (·OH) at higher temperature, e.g., 0.17, 0.23, 0.12 mmol/L of Fe^IVO²⁺ and 0.009, 0.038, 0.102 mmol/L of SO₄^·-/·OH were produced within 10 min by PSBC-600/PMS, PSBC-800/PMS, and PSBC-1000/PMS, respectively. Characterization, density functional theory (DFT) simulation and Pearson correlation analysis revealed that along with the increase of pyrolysis temperatures, the active sites of PSBC gradually shifted from atomically dispersed N-coordinated Fe moieties (FeN_x) to iron nitrides (Fe_xN), which activated PMS to produce Fe^IVO²⁺ and SO₄^·-/·OH, respectively. This study clarifies the structure-activity relationships of PSBC for PMS activation, and opens a new avenue for the treatment and utilization of PS as high value-added resources.

Keywords: Biochar; Organic pollutants degradation; Peroxymonosulfate; Pharmaceutical sludge; Pyrolysis; Reactive species.