Strong chromate-adsorbent based on pyrrolic nitrogen structure: An experimental and theoretical study on the adsorption mechanism.

Chromate is considered a toxic contaminant in various water sources because it poses a risk to animal and human health. To meet the stringent limits for chromium in water and wastewater, pyrrolic nitrogen structure was investigated as a chromate adsorbent for aqueous solutions, employing a polypyrrole coating on carbon black. The characteristics of the adsorbent were analyzed by high-resolution transmission electron microscopy, energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Chromate was adsorbed as both Cr(III) and Cr(VI). The chromate adsorption capacity increased (from 50.84 to 174.81 mg/g) with increasing amounts of pyrrole monomers (from 50 to 86%) in the adsorbent. The adsorption capacity was well-correlated with the pyrrolic nitrogen content (from 2.06 to 6.57 at%) in the adsorbent, rather than other types of nitrogen. The optimized adsorption capacity (174.81 mg/g in the equilibrium batch experiment and 211.10 mg/g at an initial pH of 3) was far superior to those of conventional adsorbents. We investigated the mechanism behind this powerful chromate adsorption on pyrrolic nitrogen via physical/chemical analyses of the pH-dependent adsorption behavior, supported by first-principles calculation based on density functional theory. We found that Cr(III) and Cr(VI) adsorption followed different reaction paths. Cr(III) adsorption occurred in two sequential steps: 1) A Jones oxidation reaction (JOR)-like reaction of Cr(VI) with pyrrolic N that generates Cr(III), and 2) Cr(III) adsorption on the deprotonated pyrrolic N through Cr(III)-N covalent bonding. Cr(VI) adsorption followed an alternative path: hydrogen-bonding to the deprotonation-free pyrrolic N sites. The pH-dependent fractional deprotonation of the pyrrolic N sites by the JOR-like reaction in the presence of chromate played an important role in the adsorption.