Synthesis of Iron(II) Clathrochelate-Based Poly(vinylene sulfide) with Tetraphenylbenzene Bridging Units and Their Selective Oxidation into Their Corresponding Poly(vinylene sulfone) Copolymers: Promising Materials for Iodine Capture (original) (raw)
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Polymers
Three organometallic copolymers, ICP1-3, containing iron(II) clathrochelate units with cyclohexyl lateral groups and interconnected by various thioether derivatives were synthesized. The reaction of the latter into their corresponding OICP1-3 sulfone derivatives was achieved quantitatively using mild oxidation reaction conditions. The target copolymers, ICP1-3 and OICP1-3, were characterized by various instrumental analysis techniques, and their iodine uptake studies disclosed excellent iodine properties, reaching a maximum of 360 wt.% (qe = 3600 mg g−1). The adsorption mechanisms of the copolymers were explored using pseudo-first-order and pseudo-second-order kinetic models. Furthermore, regeneration tests confirmed the efficiency of the target copolymers for their iodine adsorption even after several adsorption-desorption cycles.
International Journal of Molecular Sciences
Effective capture and safe disposal of radioactive iodine (129I or 131I) during nuclear power generation processes have always been a worldwide environmental concern. Low-cost and high-efficiency iodine removal materials are urgently needed. In this study, we synthesized two aniline-based hypercrosslinked polymers (AHCPs), AHCP-1 and AHCP-2, for iodine capture in both aqueous and gaseous phases. They are obtained by aniline polymerization through Friedel–Crafts alkylation and Scholl coupling reaction, respectively, with high chemical and thermal stability. Notably, AHCP-1 exhibits record-high static iodine adsorption (250 wt%) in aqueous solution. In the iodine vapor adsorption, AHCP-2 presents an excellent total iodine capture (596 wt%), surpassing the most reported amorphous polymer adsorbents. The rich primary amine groups of AHCPs promote the rapid physical capture of iodine from iodine water and iodine vapor. Intrinsic features such as low-cost preparation, good recyclability, ...
Polymers
We report the synthesis of three highly soluble metalorganic copolymers, TCP1–3, that were made from a one-pot complexation of iron(II) clathrochelate units that are interconnected by various thioether-containing contorted groups. TCP1–3 were converted into their poly(vinyl sulfone) derivatives OTCP1–3 quantitatively via the selective oxidation of the thioether moieties into their respective sulfones. All of the copolymers, TCP1–3 and OTCP1–3, underwent structural analysis by various techniques; namely, 1H- and 13C-nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). The copolymers were tested as potent lithium ions adsorbents revealing a maximum adsorption (qm) value of 2.31 mg g−1 for OTCP2. Furthermore, this same copolymer was found to be a promising adsorbent of methylene blue (MEB); an isothermal adsorption study divulged that OTCP2’s uptake of MEB from an aqueous solution (followin...
Metal Organic Framework-Polyethersulfone Composite Membrane for Iodine Capture
Polymers, 2020
A variety of metal organic frameworks (MOFs) were synthesized and evaluated for their iodine adsorption capacity. Out of the MOFs tested, ZIF-8 showed the most promising result with an iodine vapor uptake of 876.6 mg/g. ZIF-8 was then incorporated into a polymer, polyethersulfone (PES), at different proportions to prepare mixed matrix membranes (MMMs), which were then used to perform further iodine adsorption experiments. With a mixing ratio of 40 wt % of ZIF-8, the iodine adsorption capacity reached 1387.6 mg/g, wherein an astounding 60% improvement in adsorption was seen with the MMMs prepared compared to the original ZIF-8 powder.
Ferrocene-based porous organic polymers for high-affinity iodine capture
Chemical Engineering Journal, 2019
• A ferrocene-containing porous network (FcTz-POP) was synthesized by one-pot reaction. • FcTz-POP shows notably promoted iodine vapor capacity which is 1.8 times that of a reference ferrocene-free one. • We provide a simple method for strengthened binding affinity of material toward iodine.
Materials Chemistry and Physics, 2018
In the present study, the commercial polystyrene (PS, M= 350 000) was grafted with organophosphate groups via amino linkages. PS with amino groups was initially prepared by nitration and reduction reactions. Then, the aminated PS was firstly cross-linked with 2,2'-dichlorodiethylether (DCDEE), to generate a polymer named PS-NH-DCDEE, and then with tris-(2-chloroethyl) phosphate (TCEP) to get a polymer named PS-NH-TCEP. The obtained products were characterized by several methods, including FT-IR spectroscopy, thermodynamic analysis (DTA), thermogravimetric analysis (TGA), elemental analysis (EA), and X-ray diffraction (XRD) and scanning electron microscopy (SEM). The evaluation of metal cations extraction was performed by flame atomic absorption spectroscopy (FAAS) on the remaining solutions. The new cross-linked polymers were tested for their ability to extract Zn(II), Cd(II) and Fe(III) from aqueous phase at room temperature. FT-IR measurements have clearly demonstrated the interaction between metal and ligands in the matrix polymers. The new materials PS-NH-DCDEE and PS-NH-TCEP exhibited high selectivity towards Fe 3+ and Zn 2+ with levels of extraction yields between 90-98%. Although after five consecutive adsorption-desorption cycles, no obvious change in the adsorption capacity of the polymers was found, which suggests that the obtained materials were suitable for the effective removal of heavy metal ions from aqueous solutions.
Fluorescent aminal linked porous organic polymer for reversible iodine capture and sensing
Scientific Reports, 2020
A novel triazene-anthracene-based fluorescent aminal linked porous organic polymer (TALPOP) was prepared via metal free-Schiff base polycondensation reaction of 9,10-bis-(4,6-diamino-S-triazin-2-yl)anthracene and 2-furaldehyde. The polymer has exceptional chemical and thermal stabilities and exhibit good porosity with Brunauer-Emmett-Teller surface area of 401 m 2 g −1. the combination of such porosity along with the highly conjugated heteroatom-rich framework enabled the polymer to exhibit exceptional iodine vapor uptake of up to 314 wt % and reversible iodine adsorption in solution. Because of the inclusion of the anthracene moieties, the TALPOP exhibited excellent detection sensitivity towards iodine via florescence quenching with K sv value of 2.9 × 10 3 L mol −1. the cost effective TALPOP along with its high uptake and sensing of iodine, make it an ideal material for environmental remediation. Nuclear energy is becoming one of the most feasible alternative sources to meet the ever-increasing energy demand and minimize the emission of greenhouse gases because of its high-density energy, minimal carbon footprints, and low operation cost 1-4. Despite such advantages, the potential emissions of radioactive material (such as 129 I and 131 I, 3 H, 14 CO 2 , and 85 Kr) from nuclear energy power plants is a major drawback of this technology due to the serious environmental and health effect of these materials 4,5. The long-lived radionuclides of iodine, 129 I (half-life of 1.57 × 10 7 years) and 131 I (half-life of ca. 8 days), are usually emitted in the gas form which then enters the food chain through contaminated air or by depositing into soil and water. The radioactive iodine isotopes have adverse effects on human metabolic system and health, and they were indicated as major cause of thyroid cancer 5-7. Accordingly, there is an urgent need to develop new technology and means to effectively detect, capture, and store radioactive iodine. In this context, several adsorbent materials have been studied and tested for effective sequestration and sensing of iodine 4,5,8-13. It has been reported that iodine sequestration efficiency is a function of several structural properties of the adsorbent including surface area, pore size, specific high-affinity binding sites, polar groups, and conjugated units. Thus, increasing the affinity of the host to iodine, in addition to enhanced surface area, can have tremendous effect on iodine capture 4,5,14,15. Materials like activated carbon, silica, silver-doped zeolites, chalcogenide aerogels, and microporous polymers have been reported to show good adsorption capacities for radioiodine 5,16,17. However, most of these have several shortcomings such as limited surface area, high cost, low sensitivity to iodine, and difficulty in regeneration that make them quite unsuitable for practical usage 5,18-21. For example, silver-doped zeolites are expensive and have been reported to have low adsorption capacities for iodine while metal organic frameworks, in general, are unstable in humid conditions 18-22. Porous organic polymers (POPs), on the other hand, are another class of solid porous materials that have found applications in variety of areas that include gas storage and separation, catalysis, supercapacitors, light harvesting, and iodine capture 4,7,19,23-25. POPs are getting increasing attention for iodine capture due to their high surface areas, versatility in design, tunable pore size and pore volumes, excellent thermal and chemical stability, and high physiochemical robustness. As such, the chemical structures of POPs can be tailor-made to incorporate heteroatoms with expanded conjugated systems in which the lone pairs on heteroatoms and the conjugated surfaces account for strong interactions between the polymers and iodine 12,15,26,27. For example, Liu et al. reported the preparation of novel thiophene-based porous organic networks that can capture up to 204 wt.% of