Surface-bound Fe(0) and Fe(II) mediated by 2-picolinic acid functionalized zero-valent iron for highly Cr(VI) removal

Electron transfer of zero-valent iron (ZVI) is significantly impeded by its oxide layer, and limiting its removal of pollutants. In this study, 2-picolinic acid (PA) and ZVI were co-ball milled to improve electron transfer in ZVI (PA-ZVI^bm), and used for the removal of heavy metal Cr(VI). Characterization analysis showed that the presence of electron-rich groups on the surface of PA-ZVI^bm promoted the transfer of electrons from the Fe(0) core to the surface, and the surface Fe(0) and Fe(II) contents increased from 1.1 % to 6.3 % and from 60.2 % to 72.9 %, respectively, effectively reducing Cr(VI) through an electron transfer mechanism. Theoretical calculations showed that the modification of PA enhanced the adsorption of Cr(VI) on the ZVI surface, and the adsorption energy decreased from -3.561 eV to -5.119 eV. PA-ZVI^bm showed strong advantages in the removal of Cr(VI), with a reaction rate constant and adsorption capacity 17 and 13 times that of ZVI^bm, respectively, and a conversion rate of 100 %. Moreover, PA-ZVI^bm showed excellent performance over a wide pH range (3-10) and under different coexisting ions, while being cost-effective and having low environmental risks. This study explored the relationship between ZVI surface modification and performance, and provided new insights into the modification of ZVI using small molecule oxygen-containing organic acids.