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

Young Jin Ko, Keunsu Choi, Soonjae Lee, Kyung Won Jung, Seokwon Hong, Hiroshi Mizuseki, Jae Woo Choi, Wook Seong Lee

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)287-296
Number of pages10
JournalWater Research
Publication statusPublished - 2018 Nov 15


  • Chromate adsorption
  • First-principles calculation
  • Jones oxidation
  • Polarization screening
  • Pyrrolic nitrogen

ASJC Scopus subject areas

  • Ecological Modelling
  • Water Science and Technology
  • Waste Management and Disposal
  • Pollution


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