Effects of oxygen on the adsorption/oxidation of aqueous Sb(III) by Fe-loaded biochar: An X-ray absorption spectroscopy study

Abstract

Fe-loaded biochar (FeBC) has been considered for Sb(III) adsorption, but the effects of oxygen (O₂) on the adsorption need further investigation. Liquid-/solid-phase analyses were conducted to investigate the role of O₂ in the Sb(III) adsorption by FeBC. The adsorption was best described by the pseudo-second-order (PSO) model for kinetic results and by the Langmuir model for thermodynamic results. More than 96.8 % of Sb(III) was adsorbed by FeBC, and available O₂ increased the liquid-phase Sb(III) oxidation efficiency by 2.1-7.5 times. The peak changes at ~1640 and 3450 cm^-1 in FTIR spectra indicated the occurrence of inner-sphere complexation between Sb(III)/Sb(V) and hydroxyl (-OH)/carboxyl (-COOH) groups in FeBC under aerobic and anaerobic conditions. Fe/Sb X-ray absorption spectroscopy (XAS) analysis results showed aqueous Sb(III) complexed to the edge-sharing Fe(III)-O-Fe(III) in FeBC. Regardless of whether O₂ was available or not, solid-phase edge-sharing Fe(III)-O-Sb(V) complexes (~3.05 Å), which had lower toxicity and migration ability than aqueous Sb(III), formed through a ligand-to-metal charge-transfer (LMCT) process. More than 91 % of adsorbed Sb(III) was oxidized to edge-sharing Fe(III)-O-Sb(V) complexes in 3 h. Additionally, the Sb(V) from liquid-phase oxidation could also directly complex to the Fe(III)-O-Fe(III) and form edge-sharing Fe(III)-O-Sb(V) complexes. These results provide evidence to inform further FeBC application for the Sb-contaminated water treatment.

Keywords: Adsorption; Fe-loaded biochar (FeBC); Oxidation; Oxygen (O(2)); Trivalent antimony (Sb(III)); X-ray absorption spectroscopy (XAS).