Phenyl-Extended Resorcin[4]arenes: Synthesis and Highly Efficient Iodine Adsorption.

The continuous exploration of new analogs of calixarenes and pillararenes unlocks infinite opportunities in supramolecular chemistry and materials. In this work, we introduce a new class of macrocycle, phenyl-extended resorcin[4]arenes (ExR4), a unique and innovative design that incorporates unsubstituted phenylene moieties into the resorcin[4]arene scaffold. Single-crystal analysis reveals a chair-like conformation for per-methylated ExR4 (Me-ExR4) and a twisted "Figure-of-eight" shaped conformation for per-hydroxylated ExR4 (OH-ExR4). Notably, OH-ExR4 demonstrates exceptional adsorption capability toward I3 - ions in an aqueous solution, with a rapid kinetic rate of 1.18×10-2 g ⋅ mg-1 ⋅ min-1. Furthermore, OH-ExR4 shows excellent recyclability and potential as a stationary phase in column setups. The discovery of ExR4 opens up new avenues for constructing new macrocycles and inspires further research in functional adsorption materials for water pollutant removal.

Triphenylamine[3]arenes: Streamlining Synthesis of a Versatile Macrocyclic Platform for Supramolecular Architectures and Functionalities.

Triphenylamine[3]arenes (TPA[3]s), featuring [16]paracyclophane backbone with alternating carbon and nitrogen bridging atoms, were synthesized through a BF3 ⋅ Et2O-catalyzed cyclization reaction using triphenylamine derivatized monomers and paraformaldehyde. This molecular design yielded a series of TPA[3] macrocycles with high efficiency, with their facile derivatizations also successfully demonstrated. On account of the strong electron-donating properties of the TPA moieties, these TPA[3]s exhibit remarkable delayed fluorescence, and possess a significant affinity for iodine. Furthermore, their inherent three-fold symmetry rendered TPA[3]s as novel building blocks for the construction of extended frameworks and molecular cages. This advancement expands the versatility of discrete macrocycles into complex architectures, enhancing their applicability across a broad spectrum of applications.

Solvent-Responsive Nonporous Adaptive Crystals Derived from Pyridinium Hydrochloride and the Application in Iodine Adsorption.

Nonporous adaptive crystals (NACs) are crystalline nonporous materials that can undergo a structural adaptive phase transformation to accommodate specific guest via porous cavity or lattice voids. Most of the NACs are based on pillararenes because of their flexible backbone and intrinsic porous structure. Here a readily prepared organic hydrochloride of 4-(4-(diphenylamino)phenyl)pyridin-1-ium chloride (TPAPyH), exhibiting the solvent dimension-dependent adaptive crystallinity is reported. Wherein it forms a nonporous α crystal in a solvent with larger dimensions, while forming two porous ß and γ crystals capable of accommodating solvent molecules in solvent with small size. Furthermore, the thermal-induced single-crystal-to-single-crystal (SCSC) transition from the ß to α phase can be initiated. Upon exposure to iodine vapor or immersion in aqueous solution, the nonporous α phase transforms to porous ß phase by adsorbing iodine molecules. Owing to the formation of trihalide anion I2Cl- within the crystal cavity, TPAPyH exhibits remarkable performance in iodine storage, with a high uptaking capacity of 1.27 g g-1 and elevated iodine desorption temperature of up to 110 and 82 °C following the first and second adsorption stage. The unexpected adaptivity of TPAPyH inspires the design of NACs for selective adsorption and separation of volatile compound from organic small molecules.

Simple and scalable preparation of lignin based porous carbon coated nano-clay composites and their efficient removal for the diversified iodine.

Here, lignin and nano-clay were used to prepare novel composite adsorbents by one-step carbonization without adding activators for radioactive iodine capture. Specially, 1D nano-clay such as halloysite (Hal), palygorskite (Pal) and sepiolite (Sep) were selected as skeleton components, respectively, enzymatic hydrolysis lignin (EHL) as carbon source, lignin based porous carbon/nano-clay composites (ELC-X) were prepared through ultrasonic impregnation, freeze drying, and carbonization. Characterization results indicated lignin based porous carbon (ELC) well coated on the surface of nano-clay, and made its surface areas increase to 252 m2/g. These composites appeared the micro-mesoporous hierarchical structure, considerable N doping and good chemical stability. Results of adsorption experiments showed that the introduction of ELC could well promote iodine vapor uptake of nano-clay, and up to 435.0 mg/g. Meanwhile, the synergistic effect between lignin based carbon and nano-clay was very significant for the adsorption of iodine/n-hexane and iodine ions, their capacity were far exceed those of a single material, respectively. The relevant adsorption kinetic and thermodynamics, and mechanism of ELC-X composites were clarified. This work provided a class of low-cost and environmentally friendly adsorbents for radioactive iodine capture, and opened up ideas for the comprehensive utilization of waste lignin and natural clay minerals.

Highly Efficient Capture of Volatile Iodine by Conjugated Microporous Polymers Constructed Using Planar 3- and 4-Connected Organic Monomers.

The effective capture and recovery of radioiodine species associated with nuclear fuel reprocessing is of significant importance in nuclear power plants. Porous materials have been proven to be one of the most effective adsorbents for the capture of radioiodine. In this work, we design and synthesize a series of conjugated microporous polymers (CMPs), namely, TPDA-TFPB CMP, TPDA-TATBA CMP, and TPDA-TECHO CMP, which are constructed based on a planar rectangular 4-connected organic monomer and three triangular 3-connected organic monomers, respectively. The resultant CMPs are characterized using various characterization techniques and used as effective adsorbents for iodine capture. Our experiments indicated that the CMPs exhibit excellent iodine adsorption capacities as high as 6.48, 6.25, and 6.37 g g-1 at 348 K and ambient pressure. The adsorption mechanism was further investigated and the strong chemical adsorption between the iodine and the imine/tertiary ammonia of the CMPs, 3D network structure with accessible hierarchical pores, uniform micromorphology, wide π-conjugated structure, and high-density Lewis-base sites synergistically contribute to their excellent iodine adsorption performance. Moreover, the CMPs demonstrated good recyclability. This work provides guidance for the construction of novel iodine adsorbent materials with high efficiency in the nuclear power field.

Promising CO2 Capture and Effective Iodine Adsorption of Hyper-Cross-Linked Conjugated Porous Organic Polymers Prepared from a Cyclopentannulation Reaction.

Three novel conjugated porous organic polymers, denoted as C-POP1-3 and which consist of alternating pyrene cores with various contorted fluorene surrogates, were successfully synthesized from a versatile one-pot palladium-catalyzed [3+2] cyclocondensation reaction. The resulting polymers were obtained in excellent yields and displayed weight-average molecular weights (Mw) ranging from 12.2 to 20.2 kg/mol with polydispersity indices (Mw/Mn) ranging between 1.8 and 2.4, suggesting that the molecular masses are narrowly distributed and thus implying homogeneous polymer chains. Thermal stability exploration of C-POP1-3 by thermogravimetric analysis (TGA) revealed an impressive robustness with a 10% weight reduction temperature attaining 485 °C. Investigation of the inherent microporosity properties of C-POP1-3 via nitrogen adsorption experiments using Brunauer-Emmett-Teller (BET) theory discloses their surface areas which reach up to 560 m2 g-1 and pore volumes averaging 0.47 cm3 g-1. The target conjugated polymers were explored as adsorbents disclosing a maximum carbon dioxide adsorption of 83.0 mg g-1 at 273 K and low pressure for C-POP1, whereas iodine sorption tests portrayed prominent outcomes, notably for C-POP3 which proved to owe a strong affinity toward the hitherto mentioned halogen by achieving a maximum adsorption of 2220 mg g-1. Additionally, recyclability experiments confirmed the possibility to regenerate the polymers' adsorption capabilities even after seven consecutive cycles of adsorption-desorption cycles, which qualify them as auspicious iodine adsorbents.

Synthesis of Calix[4]arene-Based Porous Organic Cages and Their Gas Adsorption.

Two crystalline large-sized porous organic cages (POCs) based on conical calix[4]arene (C4A) were designed and synthesized. The four-jaw C4A unit tends to follow the face-directed self-assembly law with the planar triangular building blocks such as tris(4-aminophenyl)amine (TAPA) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) to generate a predictable cage with a stoichiometry of [6+8]. The formation of the large cages is confirmed through their relative molecular mass measured using MALDI-TOF/TOF spectra. The protonated molecular ion peaks of C4A-TAPA and C4A-TAPB were observed at m/z 5109.0 (calculated for C336H240O24N32: m/z 5109.7) and m/z 5594.2 (calculated for C384H264O24N24: m/z 5598.4). C4A-POCs exhibit I-type N2 adsorption-desorption isotherms with the BET surface areas of 1444.9 m2 ⋅ g-1 and 1014.6 m2 ⋅ g-1. The CO2 uptakes at 273 K are 62.1 cm3 ⋅ g-1 and 52.4 cm3 ⋅ g-1 at a pressure of 100 KPa. The saturated iodine vapor static uptakes at 348 K are 3.9 g ⋅ g-1 and 3.5 g ⋅ g-1. The adsorption capacity of C4A-TAPA for SO2 reaches to 124.4 cm3 ⋅ g-1 at 298 K and 1.3 bar. Additionally, the adsorption capacities of C4A-TAPA for C2H2, C2H4, and C2H6 were evaluated.

A New Porphyrin-based Covalent Organic Framework with High Iodine Capture Capacity and I-doping Enhanced Conductivity.

Covalent organic frameworks (COFs) are porous organic materials with well-defined and uniform structure. The material is an excellent candidate as a solid adsorbent for iodine adsorption. In the present study, we report the synthesis of COF with porphyrin moiety, TF-TA-COF, by solvothermal reaction, which was characterized by XRD, solid-state 13 C NMR, IR, TGA, and nitrogen adsorption-desorption analysis. TF-TA-COF showed a high specific surface area of 443 m2 g-1 , and exhibited good adsorption performance for iodine vapor, with an adsorption capacity of 2.74 g g-1 . XPS and Raman spectrum indicated that a hybrid of physisorption and chemisorption took place between host COF and iodine molecules. The electric properties of iodine-loaded TF-TA-COF were also studied. After doped with iodine, the conductivity of the material increased by more than 5 orders of magnitude. The photoconductivity of I2 -doped COF was also studied and TF-TA-COF showed doping-enhanced photocurrent generation.

Capture of Volatile Iodine Gas and Identification of Adsorption Sites in the Pore Network of Unsubstituted Imidazole Linker-Incorporated Zeolitic Imidazolate Framework-8.

The incorporation of unsubstituted imidazole (Im) in zeolitic imidazolate framework-8 (ZIF-8) crystallized in sodalite topology is proposed to improve gas capture and gas separation performance drastically. However, the incorporation of unsubstituted Im in ZIF-8 has remained challenging due to the thermodynamic instability of zinc and Im bonding in sodalite topology. We have incorporated up to 24.4 (mol %) Im linker in highly crystalline ZIF-8 with similar morphology and sodalite topology using a delayed linker addition strategy at room temperature. Im incorporation brings significant tuning to the pore architecture of ZIF-8, as confirmed by positron annihilation lifetime spectroscopy. The modifications in the pore architecture are primarily due to linker defects produced in the frameworks during crystallization and the elimination of steric hindrance due to the absence of a methyl group on Im. The Im-incorporated ZIF-8 shows significant enhancement in iodine capture as well as higher crystal structure stability under iodine vapor exposure as compared to pristine ZIF-8. Through ortho-positronium interaction with the adsorbed molecular iodine in the pore network of the frameworks, it is confirmed that iodine is preferentially adsorbed at cavity and intercrystalline voids, whereas aperture sites remain unoccupied by iodine molecules.

Iodine and Nickel Ions Adsorption by Conjugated Copolymers Bearing Repeating Units of Dicyclopentapyrenyl and Various Thiophene Derivatives.

The synthesis of three conjugated copolymers TPP1-3 was carried out using a palladium-catalyzed [3+2] cycloaddition polymerization of 1,6-dibromopyrene with various dialkynyl thiophene derivatives 3a-c. The target copolymers were obtained in excellent yields and high purity, as confirmed by instrumental analyses. TPP1-3 were found to divulge a conspicuous iodine adsorption capacity up to 3900 mg g-1, whereas the adsorption mechanism studies revealed a pseudo-second-order kinetic model. Furthermore, recyclability tests of TPP3, the copolymer which revealed the maximum iodine uptake, disclosed its efficient regeneration even after numerous adsorption-desorption cycles. Interestingly, the target copolymers proved promising nickel ions capture efficiencies from water with a maximum equilibrium adsorption capacity (qe) of 48.5 mg g-1.

Conjugated Microporous Polymers Based on Octet and Tetratopic Linkers for Efficient Iodine Capture.

Radioactive iodine from nuclear waste poses a huge threat to public safety and raises concerns about environmental pollution. There is thus a growing demand for developing novel adsorbents for highly effective iodine capture. In this work, we design and synthesize three novel conjugated microporous polymers, namely, TPE-PyTTA-CMP, TPE-TAPP-CMP, and TPE-TPDA-CMP, which are constructed by an imidization reaction based on octet and tetratopic linkers. The iodine vapor adsorption experiments show that the three CMPs have an excellent iodine adsorption capacity as high as 3.10, 3.67, and 4.68 g·g-1 under 348 K and ambient pressure conditions, respectively. The adsorbed iodine in the CMPs can be released into methanol in a dramatically rapid manner, and their excellent iodine adsorption performance can still be maintained after multiple cycles. In addition, the CMPs demonstrate good adsorption performance in an n-hexane solution of iodine, and the kinetic experimental data follow the pseudo-second-order model. The hierarchical porosity, extended π-conjugated skeleton, and rich electron-donor nitrogen sites of the CMPs could contribute to their excellent iodine adsorption performance. The knowledge information obtained in this work could open up new possibilities for designing novel CMPs targeting a wide range of environment-related applications.

Boron nitride aerogels incorporated with metal nanoparticles: Multifunctional platforms for iodine capture and detection.

Radioactive iodine vapors produced by nuclear fission can pose a significant risk to human health and the environment. Effective monitoring of iodine vapor leakage, capture and storage of radioactive iodine vapor are of great importance for the safety of the nuclear industry. Herein, we report a novel structure-function integrated solid iodine vapor adsorbent based on metal-modified boron nitride (BN) aerogel. Metal-modified BN aerogels incorporated with Cu/Ag nanoparticles (named as BN-Cu and BN-Ag, respectively) are successfully prepared by a metal-induced, ultrasonic-assisted, and in-situ transformation method. The metal-modified BN aerogels show improved mechanical properties in both of the maximum stress and residual deformation. Remarkably, due to the greatly enhanced "host-guest" and "guest-guest" effects by the introduction of metal nanoparticles, the BN-Cu and BN-Ag aerogels exhibit record-breaking iodine vapor adsorption capacities among inorganic adsorbents (1739.8 and 2234.13 wt% respectively), which are even higher than that of most organic adsorbents. Furthermore, an integrated iodine adsorption detection device based on metal-modified aerogels is constructed to realize real-time detection of the electrical properties of aerogels during iodine adsorption. This work provides a foundation for the development of BN aerogels as multifunctional platforms for effective iodine capture and detection. It also introduces new ideas for the use of structural-functional integrated materials in the prevention and control of radioactive iodine pollution.

Iodine Molecules within Triethylenediamine-Based Metal-Organic Frameworks for Hydrolysis/Alkylation Tandem Reactions.

The integration of radionuclide iodine molecules in metal-organic frameworks (MOFs) for organic synthesis is attracting considerable research attention due to their specific catalytic performance. However, understanding the comprehensive catalytic behaviors of different types of molecular iodine encapsulated in MOFs for a sequential organic transformation is a great challenge. To address this issue, we have designed two triethylenediamine-functionalized MOFs assembled from 1,3,5-tricarboxyphenyl-2-(triethylenediaminemethyl)benzene-linker and {Cd(COO)3N} or {Cu4(u3-OH)2(COO)6N} clusters. Both MOFs show good stability and adsorption of I2 in the solution and vapor phases. Catalysts obtained after treatment with ethyl acetate present efficient catalytic activity in hydrolysis/alkylation tandem reactions in water. The mechanistic investigations disclose a sequential catalytic process comprising a "hidden" Brønsted acid catalytic hydrolysis of acetals to aldehydes followed by the I2-bonding Lewis acid catalytic alkylation of aldehydes to 3,3'-disubstituted 1H-indoles.

Construction of a novel ursolic acid-based supramolecular gel for efficient removal of iodine from solution.

Pentacyclic triterpenes is a natural amphipathic product which possess a rigid backbone and several polar functional groups such as hydroxyl, carbonyl and carboxyl groups. The amphipathic character makes it easy to realize self-assemble into complex nano structure and therefore attract extensive attention due to the simple synthetic processes and renewable raw materials. Hence, a novel Ursolic acid-based hydrogel was prepared successfully via a simple self-assembly of triterpenoid derivative in methanol by capture water molecule in air. The resulting hydrogel show a porous morphology and good elasticity including strong heat resistance. Based on the characteristic above, the hydrogel showed a good iodine adsorption capacity and can removal 75.0% of the iodine from cyclohexane solution and 66.3% from aqueous solution within 36 h. Data analysis indicate that all the iodine adsorption process are dominated by chemisorption and belongs to the multi-site adsorption on heterogenous surfaces. In addition, the obtained hydrogel also possesses a good recyclability which can maintain more than 82% of its capacity after 5 cycles. The simple preparation method and easily available raw materials endow it a great potential in future pollutant treatment.

Porous organic materials for iodine adsorption.

The nuclear industry will continue to develop rapidly and produce energy in the foreseeable future; however, it presents unique challenges regarding the disposal of released waste radionuclides because of their volatility and long half-life. The release of radioactive isotopes of iodine from uranium fission reactions is a challenge. Although various adsorbents have been explored for the uptake of iodine, there is still interest in novel adsorbents. The novel adsorbents should be synthesized using reliable and economically feasible synthetic procedures. Herein, we discussed the state-of-the-art performance of various categories of porous organic materials including covalent organic frameworks, covalent triazine frameworks, porous aromatic frameworks, porous organic cages, among other porous organic polymers for the uptake of iodine. This review discussed the synthesis of porous organic materials and their iodine adsorption capacity and reusability. Finally, the challenges and prospects for iodine capture using porous organic materials are highlighted.

From Supramolecular Organic Cages to Porous Covalent Organic Frameworks for Enhancing Iodine Adsorption Capability by Fully Exposed Nitrogen-Rich Sites.

In order to overcome the limitations of supramolecular organic cages for their incomplete accessibility of active sites in the solid state and uneasy recyclability in liquid solution, herein a nitrogen-rich organic cage is rationally linked into framework systems and four isoreticular covalent organic frameworks (COFs), that is, Cage-TFB-COF, Cage-NTBA-COF, Cage-TFPB-COF, and Cage-TFPT-COF, are successfully synthesized. Structure determination reveals that they are all high-quality crystalline materials derived from the eclipsed packing of related isoreticular two-dimensional frameworks. Since the nitrogen-rich sites usually have a high affinity toward iodine species, iodine adsorption investigations are carried out and the results show that all of them display an enhancement in iodine adsorption capacities. Especially, Cage-NTBA-COF exhibits an iodine adsorption capacity of 304 wt%, 14-fold higher than the solid sample packed from the cage itself. The strong interactions between the nitrogen-rich sites and the adsorbed iodine species are revealed by spectral analyses. This work demonstrates that, utilizing the reticular chemistry strategy to extend the close-packed supramolecular organic cages into crystalline porous framework solids, their inherent properties can be greatly exploited for targeted applications.

Boost of Gas Adsorption Kinetics of Covalent Organic Frameworks via Ionic Liquid Solution Process.

Adsorption, storage, and conversion of gases (e.g., carbon dioxide, hydrogen, and iodine) are the three critical topics in the field of clean energy and environmental mediation. Exploring new methods to prepare high-performance materials to improve gas adsorption is one of the most concerning topics in recent years. In this work, an ionic liquid solution process (ILSP), which can greatly improve the adsorption kinetic performance of covalent organic framework (COF) materials for gaseous iodine, is explored. Anionic COF TpPaSO3 H is modified by amino-triazolium cation through the ILSP method, which successfully makes the iodine adsorption kinetic performance (K80% rate) of ionic liquid (IL) modified COF AC4 tirmTpPaSO3 quintuple compared with the original COF. A series of experimental characterization and theoretical calculation results show that the improvement of adsorption kinetics is benefited from the increased weak interaction between the COF and iodine, due to the local charge separation of the COF skeleton caused by the substitution of protons by the bulky cations of ILs. This ILSP strategy has competitive help for COF materials in the field of gas adsorption, separation, or conversion, and is expected to expand and improve the application of COF materials in energy and environmental science.

Polymorphic Covalent Organic Frameworks: Molecularly Defined Pore Structures and Iodine Adsorption Property.

Radioactive iodine-capturing materials are urgently needed for the emerging challenges in nuclear waste disposal. The various pore structures of covalent organic frameworks (COFs) render them promising candidates for efficient iodine adsorption. However, the detailed structure-property relationship of COFs in iodine adsorption remains elusive. Herein, two polymorphic COFs with significantly different crystalline structures are obtained based on the same building blocks with varied molecular ratios. The two COFs both have high crystallinity, high specific surface area, and excellent chemical and thermal stability. Compared with the [C4+C4] topology (PyT-2) with an AA stacking form, the [C4+C2] topology (PyT-1) with an AB stacking form has more twisted pore channels and complex ink-bottle pores. At ambient conditions, PyT-1 and PyT-2 both exhibit good adsorption properties for iodine capture either in a gaseous or liquid medium. Remarkably, PyT-1 presents an excellent maximum adsorption capacity (0.635 g g-1), and the adsorption limit of PyT-2 is 0.445 g g-1 in an n-hexane solution with an iodine concentration of 400 mg L-1, which is highly comparable to the state-of-the-art iodine absorption performance. This study provides a guide for the future molecular design strategy toward novel iodine adsorbents.

Iodine adsorption and electrochemical double-layer capacitor characteristics of activated carbon prepared from low-cost biomass.

The efficient adsorption application and electric double-layer capacitor material with low-cost biomass-based activated carbon materials have been quite common recently. In this study, chestnut shell-based activated carbons were produced by chemical activation. ZnCl2, H3PO4, and KOH agents were used for chemical activation. The obtained activated carbon, iodine adsorption from aqueous solutions, and its use as an electro capacitor were investigated. The scanning electron microscope, nitrogen adsorption/desorption, and Fourier transform infrared spectroscopy were used for characterization. The values of surface area and iodine adsorption capacity of the chestnut shell-based activated carbon are 1544 m2 g-1 and 1525 mg g-1. As a result, a specific capacitance of 97 Fg-1 with chestnut shell-based activated carbon was obtained in a 1 M KCl electrolyte for the electrochemical double-layer capacitor. This study shows that activated carbon based on the chestnut shell can be used both as an electrochemical energy storage material and as an adsorbent in iodine adsorption.

A Crosslinked Ionic Organic Framework for Efficient Iodine and Iodide Remediation in Water.

Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (≈5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer-directed synthesis of a single-crystalline ionic hydrogen-bonded crosslinked organic framework (HC OF-7). HC OF-7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed HC OF-7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L g-1 ). The high iodine/iodide removal benchmarks recorded under practical conditions make HC OF-7 a promising adsorbent for water treatment.