Development of novel adsorbents often neglects the competitive adsorption between co-occurring oxo-anions, overestimating realistic pollutant removal potentials, and overlooking the need to improve selectivity of materials. This critical review focuses on adsorptive competition between commonly co-occurring oxo-anions in water and mechanistic approaches for the design and development of selective adsorbents. Six "target" oxo-anion pollutants (arsenate, arsenite, selenate, selenite, chromate, and perchlorate) were selected for study. Five "competing" co-occurring oxo-anions (phosphate, sulfate, bicarbonate, silicate, and nitrate) were selected due to their potential to compete with target oxo-anions for sorption sites resulting in decreased removal of the target oxo-anions. First, a comprehensive review of competition between target and competitor oxo-anions to sorb on commonly used, nonselective, metal (hydr)oxide materials is presented, and the strength of competition between each target and competitive oxo-anion pair is classified. This is followed by a critical discussion of the different equations and models used to quantify selectivity. Next, four mechanisms that have been successfully utilized in the development of selective adsorbents are reviewed: variation in surface complexation, Lewis acid/base hardness, steric hindrance, and electrostatic interactions. For each mechanism, the oxo-anions, both target and competitors, are ranked in terms of adsorptive attraction and technologies that exploit this mechanism are reviewed. Third, given the significant effort to evaluate these systems empirically, the potential to use computational quantum techniques, such as density functional theory (DFT), for modeling and prediction is explored. Finally, areas within the field of selective adsorption requiring further research are detailed with guidance on priorities for screening and defining selective adsorbents.
ASJC Scopus subject areas
- Environmental Chemistry