Mechanism of Cr(VI) removal by magnetic greigite/biochar composites

This study synthesized magnetic greigite/biochar composites (MGBs) by a solvothermal method and tested their ability to remove Cr(VI) from heavy metal-polluted wastewater. X-ray diffraction (XRD), Fourier transformed infrared spectrometry (FT-IR) and scanning electron microscopy (SEM) revealed that magnetic greigite (Fe₃S₄) flakes were aggregated and anchored to the biochar surface, resulting in more active sites than pristine biochar. Maximum Cr removal efficiency and capacity of MGB-30 (greigite/biochar = 30%) at an initial Cr(VI) concentration of 20 mg/L were 93% and 23.25 mg/g, respectively. A pseudo-first-order kinetic model was determined for the Cr(VI) removal process and the Cr(VI) removal rate constants were highly dependent on the mass ratios of Fe₃S₄ loaded on biochar, initial MGB and Cr(VI) concentrations and solution pH. X-ray photoelectron spectroscopy (XPS) and flame atomic absorption spectrometric (FAAS) analysis demonstrated that Cr(VI) was preferentially adsorbed on MGBs and subsequently reduced to Cr(III) by MGBs. Electron paramagnetic resonance (EPR) spectroscopy and iron redox transformations revealed that the Cr(VI) removal enhancement was attributed to efficient surface Fe(III)/Fe(II) cycling via electron transfer with the persistent free radicals (PFRs) of biochar. These novel findings provide new insights into the Fe(III)/Fe(II) cycle induced by biochar and the prospects of using magnetic greigite/biochar composites for remediation of Cr(VI)-rich wastewaters.