Efficient reduction and adsorption of Cr(VI) using FeCl₃-modified biochar: Synergistic roles of persistent free...

Transition metal iron and persistent free radicals (PFRs) both affect the redox properties of biochar, but the electron transfer relationship between them and the coupling reduction mechanism of Cr(VI) requires further investigation. To untangle the interplay between iron and PFRs in biochar and the influences on redox properties, FeCl₃-modified rice husk biochar (FBCs) was prepared and its reduction mechanism for Cr(VI) without light was evaluated. The FBCs had higher surface positive charges, oxygen-containing functional groups, and PFRs compared with pristine rice husk biochar (BC). Phenoxyl PFRs with high electron-donating capability formed in biochar. The pronounced electron paramagnetic resonance signals showed that the PFRs preferred to form at lower Fe(III) concentrations. While a high concentration of Fe(III) would be reduced to Fe(II) and consumed the formed PFRs. Adsorption kinetics and X-ray photoelectron spectroscopy analysis indicated that the FBCs effectively enhanced the Cr(VI) removal efficiency by 1.54-8.20 fold and the Cr(VI) reduction efficiency by 1.88-9.29 fold compared to those of BC. PFRs quenching and competitive reductant addition experiments revealed that the higher Cr(VI) reduction performance of FBCs was mainly attributed to the formed PFRs, which could contribute to ∼74.0% of Cr(VI) reduction by direct or indirect electron transfer. The PFRs on FBCs surfaces could promote the Fe(III)/Fe(II) cycle through single electron transfer and synergistically accelerate ∼52.3% of Cr(VI) reduction. This study provides an improved understanding of the reduction mechanism of iron-modified biochar PFRs on Cr(VI) in environments.