Heavy Metal-Based Toxic Oxo-Pollutants Sequestration by Advanced Functional Porous Materials for Safe Drinking Water

Abstract

Water scarcity as a consequence of either environmental or economic actions is the most compelling global concern of the 21st century, as similar to 2 billion people (26% of the total population) struggle to access safe drinking water and similar to 3.6 billion (46% of the total population) lack access to clean water sanitation. In this context, groundwater pollution by toxic heavy metals and/or their oxo-pollutants, such as CrO42-, Cr2O72-, AsO43-, SeO32-, SeO42-, TcO4-, UO22+, etc., have been becoming rapidly growing global concerns. The severe toxicity upon bioaccumulation of these oxo-anions has prompted the US Environment Protection Agency (EPA) to mark these persistent and hazardous substances as priority pollutants. Additionally, the heavy-metal-based pollutants are difficult to transform into eco-friendly substances, thus presenting serious challenges toward human health and environmental preservation. To this end, the emergence of advanced functional porous materials (AFPMs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), metal-organic polyhedrons (MOPs), porous organic polymers (POPs), etc., have presented extraordinary opportunities in material research and water treatment applications. The liberty in designing and structural tunability of AFPMs, facilitated by utilization of structure-encoded molecular building blocks, enables precise control over target-specificity and structure-property correlations. Bridging the gap between strategic material design and on-demand real-world application can facilitate the development of next-generation sorbents/ion-exchangers for efficient water treatment. In this Account, we summarize the recent advancements from our group toward the development of cutting-edge multifunctional ionic-porous sorbents, offering viable solutions toward providing clean and safe drinking water. Our vision allows us to comprehend this challenge through two strategic factors: efficient oxo-anion capture via ion-exchange and specific host-guest interactions via installation of modular functional groups. To provide an overview, we first highlight the different structural variants and coexistance of various toxic oxo-anions depending on the pH of the medium and their adverse effects. Next, we highlight the promising potential of water stable cationic MOFs toward selective remediation of toxic Cr(VI), Mn(VII), Tc(VI), Se(IV), Se(VI), U (VI), As(III), and As(V)-based toxic oxo-pollutants from water. In the subsequent sections, we summarize the target-specific design strategies and oxo-anion remediation performances of ionic porous organic polymers and hybrid functional porous materials. The key role of target-specific designability and/or structural fine-tuning of AFPMs toward preferential sorption of oxo-pollutants is systematically demonstrate. Particularly, the role of ion-exchange (anion-exchange) processes toward targeted oxo-pollutant capture by ionic AFPMs has been discussed in details. In several examples, the AFPMs were successful in reducing the toxic oxo-anion concentration levels lower than the permitted values for drinking water by the World Health Organizing Committee (WHO), showcasing their real-world applicability potency.