Structural Modulation of Nitrogen-Rich Covalent Organic Frameworks for Iodine Capture.

Developing efficient adsorbent materials for iodine scavenging is essential to mitigate the threat of radioactive iodine causing adverse effects on human health and the environment. In this context, we explored N-rich two-dimensional covalent organic frameworks (COFs) with diverse functionalities for iodine capture. The pyridyl-hydroxyl-functionalized triazine-based novel 5,5',5″-(1,3,5-triazine-2,4,6-triyl)tris(pyridine-2-amine) (TTPA)-COF possesses high crystallinity (crystalline domain size: 24.4 ± 0.6 nm) and high porosity (specific BET surface area: 1000 ± 90 m2 g-1). TTPA-COF exhibits superior vapor-phase iodine adsorption (4.43 ± 0.01 g g-1) compared to analogous COF devoid of pyridinic moieties, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)-COF. The high iodine capture by TTPA-COF is due to the enhanced binding affinity conferred by the extra pyridinic active sites. Furthermore, the crucial role of long-range order in porous adsorbents has been experimentally evidenced by comparing the performance of iodine vapor capture of TTPA-COF with an amorphous network polymer having identical functionalities. We have also demonstrated the high iodine scavenging ability of TTPA-COF from the organic and aqueous phases. The mechanism of iodine adsorption by the heteroatom-rich framework is elucidated through FTIR, XPS, and Raman spectral analyses. The present study highlights the need for structural tweaking of the building blocks toward the rational construction of advanced functional porous materials for a task-specific application.

Pyridinium-Functionalized Ionic Porous Organic Polymer for Rapid Scavenging of Oxoanions from Water.

Metal oxoanions adversely affect the food chain through bioaccumulation and biomagnification. Therefore, they are among the major freshwater contaminants that require immediate remediation. Although several adsorbents are developed over the years for sequestering these micropollutants, the selective removal of oxoanions remains still a formidable challenge. Herein, pyridinium and triazine-based ionic porous organic polymer, iPOP-Cl, developed through a Brønsted acid-catalyzed aminal formation reaction, is reported as a suitable anion exchange material for the selective removal of metal oxoanions from wastewater. The positively charged nitrogen centers, along with exchangeable chloride counter-ions in the porous polymer, allow facile oxoanion uptake. iPOP-Cl is found to be a selective scavenger of permanganate (MnO4 - ) and dichromate (Cr2 O7 2- ) from water in the presence of a high concentration of competing anions generally found in brackish water. The material exhibits fast sorption kinetics, a high uptake capacity (333 mg g-1 for MnO4 - and 358 mg g-1 for Cr2 O7 2- ), and excellent recyclability.

Imidazolium and Pyridinium-based Ionic Porous Organic Polymers: Advances in Transformative Solutions for Oxoanion Sequestration and Non-redox CO2 Fixation.

The rapid pace of industrialization has led to a multitude of detrimental environmental consequences, including water pollution and global warming. Consequently, there is an urgent need to devise appropriate materials to address these challenges. Ionic porous organic polymers (iPOPs) have emerged as promising materials for oxoanion sequestration and non-redox CO2 fixation. Notably, iPOPs offer hydrothermal stability, structural tunability, a charged framework, and readily available nucleophilic counteranions. This review explores the significance of pores and charged functionalities alongside design strategies outlined in existing literature, mainly focusing on the incorporation of pyridinium and imidazolium units into nitrogen-rich iPOPs for oxoanion sequestration and non-redox CO2 fixation. The present review also addresses the current challenges and future prospects, delineating the design and development of innovative iPOPs for water treatment and heterogeneous catalysis.

Cavitand and Molecular Cage-Based Porous Organic Polymers.

Supramolecular cavitands and organic cages having a well-defined cavity and excellent host-guest complexing ability have been explored for a myriad of applications ranging from catalysis to molecular separation to drug delivery. On the other hand, porous organic polymers (POPs) having tunable porosity and a robust network structure have emerged as advanced materials for molecular storage, heterogeneous catalysis, water purification, light harvesting, and energy storage. A fruitful marriage between guest-responsive discrete porous supramolecular hosts and highly porous organic polymers has created a new interface in supramolecular chemistry and materials science, confronting the challenges related to energy and the environment. In this mini-review, we have addressed the recent advances (from 2015 to the middle of 2020) of cavitand and organic cage-based porous organic polymers for sustainable development, including applications in heterogeneous catalysis, CO2 conversion, micropollutant separation, and heavy metal sequestration from water. We have highlighted the "cavitand/cage-to-framework" design strategy and delineated the future scope of the emerging new class of porous organic networks from "preporous" building blocks.