Removal of oxytetracycline promoted by manganese-doped biochar based on density functional theory calculations: Comprehensive evaluation of the effect of transition metal doping

Abstract

The regulation of surface electrons by non-metal doping of biochar (BC) is environmentally and ecologically significant. However, systematic studies on the regulation of surface electrons by transition metal doping are lacking. The present study is based on the observation that the removal efficiency of oxytetracycline (OTC) by Mn-doped BC is eight times higher than that of undoped BC in 20 min. The effects of Mn doping on the crystal phase formation, persistent free radicals (PFRs), electron density, molecular orbitals, and nucleophilic active sites of BC are investigated, and the intermediate products of OTC are evaluated. Mn doping enhances the signal for sp²-hybridised carbon-carbon double bond, forms more delocalised π-bonds, and promotes the formation of free radicals centred on the carbon atoms. The specific surface area of BC increases, and manganese oxide is formed on the its surface. Density functional theory calculations show that Mn doping accelerates the electron transfer of BC, provides additional electrons for the BC system, and makes this system more ionised. OTC molecules preferentially attack the nucleophilic reaction sites near Mn atoms based on molecular electrostatic potential measurements. Therefore, this study provides new insights into the surface electronic structures regulated by transition metal elements.

Keywords: Biochar; Density functional theory; Manganese; Molecular electrostatic potential; Oxytetracycline.