Porous Organic Polymers Research Articles

Carbazole-Bismaleimide Based Hyper-Cross-Linked Porous Organic Polymer for Efficient Iodine Capture.

Radioactive iodine, a key waste product of nuclear energy, has been a significant concern among nuclear materials because of its high volatility and its ability to easily enter the human metabolism. Porous materials containing a large number of N-heterocyclic units such as carbazole in the skeletons use as effective adsorbents showing high iodine capture capacities. Herein, a new carbazole-bismaleimide-based hyper-cross-linked porous organic polymer (CzBMI-POP) was successfully prepared from a new tetra-armed carbazole-maleimide monomer (Bis-Cz(BMI)), which contains biscarbazole units and maleimide side groups. To produce CzBMI-POP, a free radical polymerization reaction was carried out via the unsaturated double bonds of Bis-Cz(BMI), enabling the construction of the N-rich porous skeleton in a simple and practical way. A high surface area carbazole-bismaleimide-based POP with polymer backbone having affinity for iodine uptake and sponge-like pore structures ranging from 2 to 20 nm showed iodine uptake capacity up to 215 wt %. The study highlights new opportunities to use POPs as iodine capture platform from nuclear waste, highlighting their potential for environmental remediation due to their easy synthesis and low cost.

Photocatalytic Oxidation of Sulfides in Water Using a Donor–Acceptor-Based Porous Organic Polymer

Photocatalytic Oxidation of Sulfides in Water Using a Donor–Acceptor-Based Porous Organic Polymer

Imidazolium-Functionalized Ionic Porous Organic Polymer for Efficient Removal of Oxo-Anions Pollutants from Water

The development of highly efficacious materials for the removal of toxic heavy metal-based oxo-anions is of utmost importance. Herein, an ionic porous organic polymer (designated as HB-IPOP) was synthesized through a quaternization reaction between hexa(imidazole-1-yl)benzene and 5,5′-Bis(bromomethyl)-2,2′-bipyridine. HB-IPOP exhibited high saturation uptake capacities, specifically 292 mg·g−1 for Cr2O72− and 531 mg·g−1 for ReO4−, and demonstrated exceptional selectivity for both Cr2O72− and ReO4−. Additionally, HB-IPOP demonstrates high recyclability, allowing its reuse over at least five cycles. DFT calculations confirmed that the superior interaction sites and binding energies of HB-IPOP with Cr2O72− and ReO4− outperform the affinities of other competing anions. This theoretical validation aligns with the experimentally observed high capacity and selectivity of HB-IPOP for these oxo-anions. Hence, HB-IPOP emerges as a promising candidate to replace current adsorbent materials in the effective removal of Cr2O72− and TcO4− anions from water.

Porous Organic Polymers Incorporating Shape‐Persistent Cyclobenzoin Macrocycles for Organic Solvent Separation

AbstractThe recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape‐persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np‐POP) and the corresponding model compound by reacting the cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5‐tetraaminobenzene and 1,2‐diaminobenzene, respectively, under solvothermal conditions. Co‐crystallization of the macrocycle and the model compound with various solvent molecules revealed their size‐selective inclusion within the macrocycle. Building on this finding, the np‐POP with a hierarchical pore structure and a surface area of 579 m2 g−1 showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm – such as acetonitrile and dichloromethane – showed high uptake capacities exceeding 7 mmol g−1. Xylene separation tests revealed a high overall uptake (~34 wt %), with o‐xylene displaying a significantly lower uptake (~10 wt % less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents.

Phenolic Resin-type Microporous Organic Polymers for High-Performance Carbon Capture.

Three new types of Si-centered porous organic polymer (Si-POPs) were successfully prepared using phenolic resin-type chemistry to form C-C bonds. This new family of microporous Si-POPs manifests as uniform, microporous, spherical particles with a high specific surface area. Notably, Si-POPs were engineered to possess varying numbers of hydroxyl (-OH) groups by altering the monomer in the synthetic process. Among these materials, the variant with the highest number of hydroxyl groups exhibited ultra-high CO2 adsorption capacity, reaching up to 4.3 mmol g-1 at 273 K and 1.0 bar, which surpasses the performance of most porous polymers. Furthermore, Si-POPs also demonstrated remarkable selectivity adsorption for carbon dioxide over nitrogen (17-50, IAST at 273 K and 1.0 bar). This study not only highlighted the superior CO2 adsorption properties of Si-POPs but also explored their potential application in selective CO2 adsorption.

In-Situ Formation of Three-Dimensional Network Intrinsic Microporous Ladder Polymer Membranes with Ultra-High Gas Separation Performance and Anti-Trade-Off Effect.

The global quest for clean energy and sustainable processes makes advanced membrane extremely attractive for energy-intensive industrial gas separations. Here, we disclosed a series of ultra-high-performance gas separation membranes (PIM-3D-TB) from novel network polymers of intrinsic microporosity (PIM) that combine the advantages of solution processible PIM and small pore size distribution (PSD) of porous organic polymers (POP), which was synthesized by in situ copolymerization of triptycene-2,6-diamine as linear part and triptycene-2,6,13(14)-triamine (TTA) as crosslinker. The resulting PIM-3D-TB membranes demonstrated outstanding separation properties that outperformed the latest trade-off lines for H2/CH4 and O2/N2. They also showed an anti-trade-off effect by simultaneously enhancing gas permeability and gas-pair selectivity with increasing TTA content. The TTA crosslinking node increased the microporosity, and, shifted the PSD from the ultramicropore (<7 Å) toward the more size sieving submicropore (<4 Å) region. The post-treated TTA-75 displayed an exceptional H2 permeability of 8000 Barrer and H2/CH4 selectivity of 208. These PIM-3D-TB membranes and their design protocol have unparalleled potential in the next generation of membranes for hydrogen purification and air separations.

Porous Organic Polymers Incorporating Shape-Persistent Cyclobenzoin Macrocycles for Organic Solvent Separation.

The recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape-persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np-POP) and the corresponding model compound by reacting the cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5-tetraaminobenzene and 1,2-diaminobenzene, respectively, under solvothermal conditions. Co-crystallization of the macrocycle and the model compound with various solvent molecules revealed their size-selective inclusion within the macrocycle. Building on this finding, the np-POP with a hierarchical pore structure and a surface area of 579 m2 g-1 showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm - such as acetonitrile and dichloromethane - showed high uptake capacities exceeding 7 mmol g-1. Xylene separation tests revealed a high overall uptake (~34 wt %), with o-xylene displaying a significantly lower uptake (~10 wt % less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents.

Rapid and Scalable Preparation of High‐Crystalline Carboxyl‐Functionalized Covalent Triazine Frameworks via Friedel‐Crafts Reaction

The Friedel‐Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel‐Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel‐Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time. Theoretical calculations and detailed experiments revealed the critical role of carboxyl groups in aromatic benzene monomer during the CTFs crystallization, which can not only effectively cause a suitable activation barrier for the electrophilic attack of 2,4,6‐trichloro‐1,3,5‐triazine through their electron‐withdrawing properties, but also introduce anchoring effects (molecular confinement effects) to facilitate the ordered polymerization at specific sites in 2D planar direction. Benefiting from the convenient synthetic route and low‐cost raw materials, we could unprecedentedly realize the kilogram‐scale fabrication of carboxyl‐functionalized high‐crystalline CTFs. Moreover, thanks to the hydrophilic and ionizable properties of carboxyl groups, the obtained functionalized CTFs exhibited excellent aqueous dispersibility and superior solution processability.

Rapid and Scalable Preparation of High-Crystalline Carboxyl-Functionalized Covalent Triazine Frameworks via Friedel-Crafts Reaction.

The Friedel-Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel-Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel-Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time. Theoretical calculations and detailed experiments revealed the critical role of carboxyl groups in aromatic benzene monomer during the CTFs crystallization, which can not only effectively cause a suitable activation barrier for the electrophilic attack of 2,4,6-trichloro-1,3,5-triazine through their electron-withdrawing properties, but also introduce anchoring effects (molecular confinement effects) to facilitate the ordered polymerization at specific sites in 2D planar direction. Benefiting from the convenient synthetic route and low-cost raw materials, we could unprecedentedly realize the kilogram-scale fabrication of carboxyl-functionalized high-crystalline CTFs. Moreover, thanks to the hydrophilic and ionizable properties of carboxyl groups, the obtained functionalized CTFs exhibited excellent aqueous dispersibility and superior solution processability.

Catalysis of a LiF-rich SEI by aromatic structure modified porous polyamine for stable all-solid-state lithium metal batteries.

Poly(ethylene oxide) (PEO)-based solid-state polymer electrolyte (SPE) is a promising candidate for the next generation of safer lithium-metal batteries. However, the serious side reaction between PEO and lithium metal and the uneven deposition of lithium ions lead to the growth of lithium dendrites and the rapid decline of battery cycle life. Building a LiF-rich solid electrolyte interface (SEI) layer is considered to be an effective means to solve the above problems. Here, porous organic polymers (POPs) with aromatic structures and non-aromatic structures were synthesized and introduced into the PEO-based SPE as fillers to explore the effect of aromatic structures on LiF-rich SEI formation. The results show that the POPs containing aromatic groups could catalyze the decomposition of LiTFSI to form a stable LiF-rich SEI layer and inhibit the growth of lithium dendrites. The discharge capacity of the LFP/Li battery is 103 mA h g-1 after 500 cycles at 1C (100 °C). It provides a promising way to improve the stability of the solid electrolyte matrix and SEI layer.

Unveiling the Potential of Thiophene-Functionalized Porous Organic Polymers for Bromine Adsorption and Selective Separation from Iodine.

Bromine is a significant environmental threat due to its corrosive nature and contribution to ozone layer depletion. It often coexists with iodine and forms interhalogen complexes (IBr), which require an effective and selective bromine adsorption strategy. Leveraging the electrophilic nature of bromine, we designed an electron-rich thiophene-based porous organic polymer (POF-2). This material exhibits exceptional efficiency for bromine adsorption (2.86 g g-1) and rapid uptake kinetic from aqueous solutions, driven by noncovalent charge transfer interactions. POF-2 also demonstrates selective capture of bromine from a bromine-iodine mixture in cyclohexane. The material's electron-rich sites exhibit a stronger orbital interaction with the σ* orbital of bromine compared to iodine, leading to the observed selectivity in cyclohexane.

Design and synthesis of tetralactam macrocycle-based porous organic polymers (POPs): application in the recovery of gold from e-waste

Tetralactam macrocycles that selectively bind gold ions have been exploited to construct porous organic polymers (POPs) and the capabilities of the latter for gold adsorption are demonstrated.

Efficient CO2 hydrogenation to formate with iridium catalyst supported by porous organic polymer containing N-phenyl-picolinamide motif

Development of highly efficient catalysts for CO2 hydrogenation is crucial for the utilization of CO2. In this work, two novel heterogeneous porous organic polymer (POP)-supported iridium catalysts (Cat-1 and Cat-2)...

Modulating the electronic interaction between Au and nitrogen-rich porous organic polymers for enhanced CO2 hydrogenation to formic acid

Au nanoparticles supported on the amine functionalized porous organic polymers show efficient CO2 activation and hydrogenation to formic acid.

Efficient construction of high-quality sulfonated porous aromatic frameworks by optimizing the swelling state of porous structures.

Conventional post-modification methods usually face the fundamental challenge of balancing the high content of functional groups and large surface area for porous organic polymers (POPs). The reason, presumably, stems from ineffective and insufficient swelling of the porous structure of POP materials, which is detrimental to mass transfer and modification of functional groups, especially with large-sized ones. It is important to note that significant differences exist in the porous structures of POP materials in a solvent-free state after thermal activation and solvent swelling state. Herein, we propose that the improvement of the swelling state of the porous structure of POP materials is more conducive to obtaining high-quality sulfonated POP materials, and employ a one-pot modification strategy for preparing sulfonated porous aromatic frameworks (PAFs) to prove the proposal. These results show that the specific surface area of the resulting polymer is 580 m2 g-1 with a sulfur content of up to 13.2 wt%, which is superior to most sulfonated porous materials and the control sample. More importantly, we have also shown that the same conclusion is reached by performing similar treatments on hyper-crosslinked polymers (HCPs) and conjugated microporous polymers (CMPs), proving that our hypothesis is effective and feasible when compared to the conventional post-sulfonation method. The excellent hydrophilicity, rich content of sulfonic acid groups, high specific surface area and hierarchical pore structure make the resulting polymer an ideal adsorbent for micro-pollutants in water. The maximum adsorption capacities for Rhodamine B (RhB), Methylene Blue (MB), Tetracycline (TC) and Ciprofloxacin (CIP) are 1075 mg g-1, 1020 mg g-1, 826 mg g-1 and 1134 mg g-1, respectively. This study not only demonstrates the preparation of efficient sulfonated porous adsorbents for the efficient removal of cationic dyes and antibiotics but also illustrates an effective method for constructing high-quality functional POP materials by optimizing the swelling state of the porous structure.

5,12-Dihydroquinoxalino[2,3-b] quinoxaline-based porous organic polymer as photocatalyst for visible-light-driven cross-coupling reactions

5,12-Dihydroquinoxalino[2,3-b] quinoxaline-based porous organic polymer as photocatalyst for visible-light-driven cross-coupling reactions

Engineering iodine decorated azo-bridged porous organic polymer: A brilliant catalyst for the preparation of 2,4,6-trisubstituted pyridines

Iodine catalysis in organic transformations affords detailed coverage of recent advances in iodine chemistry. In this direction, the azo-bridged porous organic polymer bearing triazine and phloroglucinol moieties (Azo-POP1) was constructed via interfacial azo-coupling polymerization in water at room temperature. Considering its high specific surface area (153 m2.g-1) and pore size of 2.2 nm, karyotype-like morphology and considerable surface wettability, Azo-POP1 was successfully used as an adsorbent of I2. The adsorption kinetics studies show that the adsorption reaches equilibrium within one hour and increases with temperature. To our delight, this system (I2@Azo-POP1) was used as an irreplaceable heterogeneous catalyst for the synthesis of 2,4,6-trisubstituted pyridines via condensation reaction of diverse ketones with benzylamine and the following cyclization and cooperative vinylogous anomeric based oxidation. All the products were prepared in good yields under mild reaction conditions. Also, this attitude benefits from the environmentally friendly and recyclability of described catalyst.

Rational decoration of porous organic polymers with silver nanoparticles for strategic reduction of hazardous nitroaryl compounds

We offer a rational study of simple synthesis of porous organic polymers which impregnate their own reducing sites of Ag+ into Ag nanoparticles at the meantime we utilized these nanocomposites for reducing hazardous pollutants.

Constructing a cationic porous organic polymer with [PF6]- charge-balanced anion for a rapid, selective and high-capacity thorium capture

Constructing a cationic porous organic polymer with [PF6]- charge-balanced anion for a rapid, selective and high-capacity thorium capture

A Chiral Porous Organic Polymer Used as the Stationary Phase for High-Resolution Gas Chromatography Separations.

A chiral porous organic polymer (cPOP) was synthesized through nucleophilic substitution polymerization between dichloromaleimide and aromatic amine. This cPOP was used as a new chiral stationary phase (CSP) for gas chromatography (GC) chiral separation. In this work, we first used this cPOP as the CSP for gas chromatography to investigate its ability to separate racemic mixtures, including amino acid derivatives, chiral alcohols, aldehydes, alkanes, ketones, esters, and organic acids. The results showed that the column can effectively separate various racemic mixtures and achieve baseline separation of threonine (Rs = 1.91). Furthermore, the separation mechanism was elucidated by density functional theory (DFT) simulation. Additionally, the cPOP column demonstrated good repeatability and stability. The relative standard deviations (RSDs) for intraday were 0.11%-0.12% (n = 3) for the retention time of n-butyl glycidyl ether, 0.1%-0.34% (n = 3) for interday, and 2.25%-3.37% (n = 3) for column to column. This work shows that cPOP has good potential as chiral stationary phases in gas chromatography.