Toward a mechanistic understanding of Rhenium(VII) adsorption behavior onto aminated polymeric adsorbents: Batch experiments, spectroscopic analyses, and theoretical computations

Abstract

Rhenium, a rare and critical metal, existing in the industrial wastewater has been aroused extensive interests recently, due to its environmental and resource issues. Chitosan, an easily available, low-cost and eco-friendly biopolymer, was prepared and modified by grafting primary, secondary, tertiary and quaternary amino groups, respectively. Adsorption behaviors and interactions between ReO4− and these four types of aminated adsorbents were investigated through batch experiments, spectroscopic analysis, and theoretical computations. Chitosan modified with secondary amines showed an extremely high uptake of ReO4− with 742.0 mg g−1, which was higher than any reported adsorbents so far. Furthermore, a relatively high adsorption selectivity for Re(VII), as well as the stable and facile regeneration of these aminated adsorbents revealed a promising approach for Re(VII) recovery in full-scale applications. The electrostatic attraction was illustrated to be the main adsorption mechanism by Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy analyses. Significantly, the sub-steps of the adsorption process, encompassing the transformation of binding sites and the subsequent binding between these sites and the adsorbate, have been thoroughly investigated through the density functional theory (DFT) calculation method. This approach was firstly proposed to clearly demonstrate the differences in Re(VII) adsorption behavior onto four types of aminated adsorbents, resulting the importance of not only strong binding energy but also an appropriate binding spatial environmental for effective Re(VII) adsorption.