Optimization and mechanisms of methylene blue removal by foxtail millet shell from aqueous water and reuse in biosorption of Pb(II), Cd(II), Cu(II), and Zn(II) for secondary times

Abstract

Foxtail millet shell as a raw efficient adsorbent was chosen first to eliminate methylene blue (MB) based on the uneven surface with many micropores, lots of negative charges, various functional groups, and some primary elements. And then the adsorbent-loaded MB was used to remove Pb(II), Cd(II), Cu(II), and Zn(II) from aqueous water for secondary adsorption. The effects of various factors were explored and optimized for removal rates of MB on the surface of the adsorbent using response surface methodology (RSM). After these factors were optimized, the confirmed removal rates of MB by the adsorbents were reached at 92.04, 93.05, and 93.36%, respectively from aqueous water while the solution pH was at 3, 7, and 11, respectively. The behavior of adsorption for MB dye was well-described by Langmuir isotherm (R 2 = 0.9951), demonstrating favorable monolayer adsorption of MB on the adsorbent with the maximum capacity of 165.07 mg·L−1 in aqueous water. The data of MB dye removal was better assessed by pseudo-second-order model (R 2 ≥ 0.9033), indicating an exchange of electrons has occurred between the adsorbent and MB particles, especially K and Ca ions of the adsorbent. In addition, the adsorbent-loaded MB has still presented better adsorption abilities for Pb(II), Cd(II), Cu(II), and Zn(II), respectively after MB removal in aqueous water. The adsorption mechanisms of adsorption were explored with the characterizations of the adsorbent before and after adsorption for the target pollutants by the methods of TEM, SEM, nitrogen physisorption isotherms, XPS, EDS, IR, and zeta potential classes. In summary, the results presented that the foxtail millet shell could be applied to remove MB dye effectively from aqueous water with the combined effects of electrostatic attraction, ion exchange, functional groups binding, and pore diffusion, but also, the adsorbent loaded with MB can be still applied to eliminate Pb(II), Cd(II), Cu(II), and Zn(II) by effects of electrostatic attraction and functional groups complexation in aqueous water. Novelty Statement In the present work, (a) the raw foxtail millet shell as a new potential adsorbent was used to remove MB dye from aqueous water for the first times, and operational variables of adsorption MB were investigated and optimized using response surface methodology, (b) the foxtail millet shell loaded MB as a disused adsorbent without any chemical reagent added was carried out to remove Pb(II), Cd(II), Cu(II), and Zn(II) ions, respectively in aqueous water for a secondary cycle, (c) adsorption mechanisms of MB removal on the adsorbent and the target heavy metals on the disused adsorbent were explored by the various analytical methods. This work provides evidence for the adsorption of MB on the natural adsorbent and improves the utilization efficiency of the used adsorbent on Pb(II), Cd(II), Cu(II), and Zn(II) removal in aqueous water.