Structural design, preparation and characterization of light, isotropic and robust statically determined organic frameworks as reusable adsorbents

Synthesis of phenothiazine-based porous organic polymer and its application to iodine adsorption

Carbon-carbon coupling is a basic design principle for the synthesis of porous organic polymers, which are widely used in gas adsorption/separation, photocatalysis, energy storage, etc. However, the C(sp3)-C(sp3) coupling reaction to construct porous organic polymers remains an important yet elusive objective due to its low reactivity and unknown side reactions. Herein, we report that nickel bis(1,5-cyclooctadiene) (Ni(COD)2), which was a famous catalyst for C(sp2)-C(sp2) coupling reactions, enables highly efficient C(sp3)-C(sp3) homo-coupling reactions to construct porous linear crystalline polymers and flexible three-dimensional porous aromatic frameworks (PAFs) under mild reaction conditions. The resulting linear polymers generated with dibromomethyl arenes have good crystallinity and high melting points (T m = 286 °C) due to controllability of reaction sites. Furthermore, the PAFs (PAF-64, PAF-65 and PAF-66) stemmed from tri-/tetra-bromomethyl arenes show high surface area (S BET = 390 m2 g-1) and high methane-storage capacity (up to 313 cm3 cm-3) because of their flexible frameworks. This work sheds new light on the construction of novel porous polymers through C(sp3)-C(sp3) coupling reactions and the development of methane-storage materials.

Copper-incorporated porous organic polymer as efficient and recyclable catalyst for azide-alkyne cycloaddition

Porous organic polymers with different pore structures for sensitive solid-phase microextraction of environmental organic pollutants

Efficient capture of CO2 and its conversion into other high value-added compounds by electrochemical methods is an effective way to reduce excess CO2 in the atmosphere. Porous polymeric materials hold great promise for selective adsorption and electrocatalytic reduction of CO2 due to their high specific surface area, tunable porosity, structural diversity, and chemical stability. Here, we review recent research advances in this field, including design of porous organic polymers (POPs), porous coordination polymers (PCPs), covalent organic frameworks (COFs), and functional nitrogen-containing polymers for capture and electrocatalytic reduction of CO2. In addition, key issues and prospects for the optimal design of porous polymers for future development are elucidated. This review is expected to shed new light on the development of advanced porous polymer electrocatalysts for efficient CO2 reduction.

Modulating pore microenvironment in a robust ionic porous polymer for efficient propyne/propylene separation

Porous organic polymers (POPs) show enormous potential for applications in separation, organic electronics, and biomedicine due to the combination of high porosity, high stability, and ease of functionalisation. However, POPs are usually insoluble and amorphous materials making it very challenging to obtain structural information. Additionally, important parameters such as the exact molecular structure or the crosslinking degree are largely unknown, despite their importance for the final properties of the system. In this work, we introduced the reversible multi-fold nitroxide exchange reaction to the synthesis of POPs to tune and at the same time follow the crosslinking degree in porous polymer materials. We synthesised three different POPs based on the combination of linear, trigonal, and tetrahedral alkoxyamines with a tetrahedral nitroxide. We could show that modulating the equilibrium in the nitroxide exchange reaction, by adding or removing one nitroxide species, leads to changes in the crosslinking degree. Being able to modulate the crosslinking degree in POPs allowed us to investigate both the influence of the crosslinking degree and the structure of the molecular components on the porosity. The crosslinking degree of the frameworks was characterised using EPR spectroscopy and the porosity was determined using argon gas adsorption measurements. To guide the design of POPs for desired applications, our study reveals that multiple factors need to be considered such as the structure of the molecular building blocks, the synthetic conditions, and the crosslinking degree.

Porous organic polymers (POPs) offer exceptional surface area, tunable pore sizes, and versatile chemical functionality, making them attractive for a range of advanced applications. However, their conventional powdered form limits processability, structural integration, and practical deployment. Integrating POPs into fibrous matrices through electrospinning, a scalable and versatile technique for producing nonwoven fibers, helps overcome these limitations and enables the creation of new material architecture. The resulting POP-incorporated fibrous materials (POP-FMs) combine the intrinsic advantages of POPs with enhanced mechanical integrity, tailored surface properties, and improved mass transport characteristics. These features expand the potential of POP-FMs in areas such as catalysis, environmental remediation, sensing, and biomedical fields. This review discusses recent progress in the design and synthesis of electrospinning-compatible POPs, strategies for fabricating POP-FM composites, and the structure-property relationships that govern their performance. Key challenges and future directions are also explored, underscoring the potential of POP-FMs as next-generation functional materials.

Chemical warfare agents (CWAs) have been a consistent a global concern with regard to both defence and civilian safety. In order to safeguard people from these harmful chemicals, numerous research teams have collaborated with defence organizations to find an advanced technological solution in terms of effectiveness and strength. In this context, porous organic polymers (POPs) have been thoroughly investigated as an ideal option for catalytically detoxifying CWAs by initially capturing them and subsequently transforming them into harmless chemicals. POPs are a new category of porous organic material, primarily made up of organic components linked by robust covalent bonds, resulting in highly interconnected frameworks with firm structures and defined voids for housing guest molecules. This review article offers a summary of current studies concerning different synthetic methods for POPs (HCPs, PIMs, and certain amorphous POPs), potential modifications to their functionality, and their promising use in photocatalytic/thermal detoxification of chemical warfare agents (CWAs). This review underscores the need for ongoing research to create effective, safe, and ecofriendly decontamination techniques. Ultimately, various catalytic processes of detoxification like hydrolysis and oxidation have been explored with POPs, and mechanisms were established through structure-activity relationships with various novel techniques. Additional needs and potential applications of utilizing POPs as nanoreactors for the detoxification of CWAs are also discussed.

Multifunctional porous organic polymers (POPs): Inverse adsorption of hydrogen over nitrogen, stabilization of Pd(0) nanoparticles, and catalytic cross-coupling reactions and reductions

Herein, we present two novel ferrocene-containing porous organic polymers, FPOP-1 and FPOP-2, by the Heck reactions of 1,1′-divinylferrocene with two tetrahedral silicon-centered units, i.e., tetrakis(4-bromophenyl)silane and tetrakis(4′-bromo-[1,1′-biphenyl]-4-yl)silane. The resulting materials possess high thermal stability and moderate porosity with the Brunauer–Emmer–Teller (BET) surface areas of 499 m2 g−1 (FPOP-1) and 354 m2 g−1 (FPOP-2) and total pore volumes of 0.43 cm3 g−1 (FPOP-1) and 0.49 cm3 g−1 (FPOP-2). The porosity is comparable to previously reported ferrocene-containing porous polymers. These materials possess comparable CO2 capacities of 1.16 mmol g−1 (5.10 wt%) at 273 K and 1.0 bar, and 0.54 mmol g−1 (2.38 wt%) at 298 K and 1.0 bar (FPOP-1). The found capacities are comparable to, or higher than many porous polymers having similar or higher surface areas. They have high isosteric heats of up to 32.9 kJ mol−1, proving that the affinity between the polymer network and CO2 is high, which can be explained by the presence of ferrocene units in the porous networks. These results indicate that these materials can be promisingly utilized as candidates for the storage or capture of CO2. More ferrocene-containing porous polymers can be designed and synthesized by combining ferrocene units with various aromatic monomers under this strategy and their applications could be explored.

A new triazine-thiophene based porous organic polymer as efficient catalyst for the synthesis of chromenes via multicomponent coupling and catalyst support for facile synthesis of HMF from carbohydrates

In recent years, the flexibility of porous organic polymers has demonstrated very unique properties during their applications. This paper reports a novel soluble porous polymer (named BIT-POP-75 and BIT-POP-75-OH) with 1,2-diketone and 1,2-diol subunits in the flexible polymer chain using contorted subunits. The solubility of the porous polymer and the flexible chelating 1,2-diol moiety facilitates the high loading and uniform dispersion of Pd nanoparticles to give the catalyst Pd@BIT-POP-75-OH, which shows high efficiency (kapp = 0.965 min-1) for the catalytic reduction of 4-nitrophenol with good recyclability (10 cycles).

A series of porous organic polymers (POPs) based on N-heterocyclic carbene (NHC) building blocks has been prepared through an octacarbonyldicobalt complex [Co2 (CO)8 ]-catalyzed trimerization of terminal alkyne groups. By changing the monomer ratio in the copolymerization, cross-linked POPs with tunable surface areas of 485-731 m2 g-1 and pore volumes of 0.31-0.51 cm3 g-1 were easily prepared. Compared with the analogues homogeneous NHC (SIPr) catalysts, the POPs exhibited an enhanced catalytic activity and high selectivity in the reductive functionalization of CO2 with amines. The extraordinary performance of the sample could be attributed to the combination of the gas enrichment (or storage) effect, enhanced in-pore concentrations of other substrates, and advantageous micropore structures of the porous polymers. Meanwhile, these catalysts can easily be separated and recycled from the reaction systems with only a slight loss of activity. This excellent catalytic performance and facile recycling of heterogeneous catalysts make them very attractive. These NHC-containing POPs may provide a new platform for catalytic transformations of CO2 .

ABSTRACTWater contamination resulting from organic dyes has had severe detrimental effects on human health and environmental tolerance. To address this issue, a delicate strategy for taking host–guest function in porous organic polymers via a facile Friedel–Crafts reaction of triptycene and post‐modification was achieved. By means of this route, a sulfonic acid functionalized triptycene‐based porous organic polymer (TPOP–SO3H) with a hierarchical structure and a desirable Brunauer–Emmett–Teller value of 1002 m2/g was synthesized this study. The TPOP–SO3H material demonstrated a maximum adsorption capacity for methylene blue of 97.1 mg/g. Remarkably, an absorption efficiency of more than 90% of TPOP–SO3H was observed even after five cycles. Therefore, such a hierarchical porous organic polymer can be highly recommended as one type of promising material for the treatment of organic dye‐polluted wastewater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47987.