Task-specific synthesis of novel indole-based porous organic polymers for carbon dioxide adsorption and iodine uptake

A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

Superior Iodine Uptake Capacity Enabled by an Open Metal-Sulfide Framework Composed of Three Types of Active Sites

聚咔唑具有刚性主链和共轭富电子体系, 既有利于形成永久性多孔材料, 又可增强被吸附物与吸附剂之间的相互作用, 还具有特异的光电性能. 因此, 近年来有机多孔聚咔唑材料的研究成为有机多孔材料领域中的一个热点. 有机多孔聚咔唑一般具有较大的比表面积和稳定的孔结构, 其制备方法简单多样, 多孔性可调控, 而且可以保持良好的光学电学性质, 在气体存储与分离、有机蒸气吸附、催化、传感及有机电子学等方面具有潜在的应用价值. 就有机多孔聚咔唑材料的制备而言, 常用的制备方法是以氧化偶联反应和Friedel-Crafts反应为代表的合成方法, 还有一些如氰基三聚和碳–碳偶联反应等其他的合成方法. 本文主要介绍近几年有机多孔聚咔唑的制备方法和性能研究与应用方面的最新进展.

Porous organic polymers (POPs) are a class of materials composed of organic building blocks usually consisting of the elements C, H, O, N, and B and other light elements connected by covalent bonds. Owing to the diversity of synthesis methods in organic chemistry, POPs can be prepared by Suzuki coupling, Sonogashira-Hagihara cross-coupling, Schiff-base condensation, Knoevenagel condensation, and Friedel-Crafts alkylation. POPs show great application potential in the field of sample pretreatment because of their large specific surface area, adjustable pore size, high tailorability, and easy modification. The design of new functional building blocks is an important factor in advancing the development of POPs and is key to the efficient separation and enrichment of target molecules in complex substrates. In recent years, supramolecular-derived compounds have provided new inspiration and breakthroughs in the construction of POPs on account of their excellent host-guest recognition properties, simple functionalization strategies, and adjustable topological configurations. The "cavitand-to-framework" approach, that is, the knitting of 0D macrocycles into hierarchical 2D or 3D POPs using suitable linkers, and extension of the research scope of supramolecular chemistry from discrete cavities to rigidly layered porous organic frameworks can lead to significant improvements in the porosity and stability of supramolecular-derived compounds. They can also provide an effective means to expand the structural diversity of POPs and generate layered structures with high porosity. This review summarizes the preparation strategies and structural characteristics of supramolecular-derived POPs with different structures, such as crown ether-based POPs, cyclodextrin-based POPs, and calixarene-based POPs. The promising applications of these materials in sample pretreatment focusing on food analysis and environmental monitoring, including epoxides, organic dyes, heavy metals, algatoxins, halogens, and antibiotic drugs, are then summarized. Next, the extraction mechanisms mainly attributed to host-guest recognition, π-π stacking, and hydrogen-bonding and electrostatic interactions between the supramolecular structures and analytes are described. The key role and potential advantages of the different preparation strategies and structural characteristics of these POPs in sample pretreatment are also discussed. Finally, the future prospects and remaining challenges of supramolecular-derived POPs are proposed. Supramolecular-derived POPs can not only achieve the rapid and selective extraction of target analytes during sample pretreatment but also improve the extraction effect of online solid phase extraction technologies. However, although numerous supramolecular-derived POPs have been developed, few have been applied in the field of sample pretreatment. Thus, the expansion of the application potential of more POP materials requires further exploration and research. The design and synthesis of supramolecular-derived POPs with highly selective recognition performance remains an important research direction in the field of sample pretreatment.

Design and successful synthesis of phenolic-OH and amine-functionalized porous organic polymers as adsorbent for postcombustion CO2 uptake from flue gas mixtures along with high CO2/N2 selectivity is a very demanding research area in the context of developing a suitable adsorbent to mitigate greenhouse gases. Herein, we report three triazine-based porous organic polymers TrzPOP-1, -2, and -3 through the polycondensation of two triazine rings containing tetraamine and three dialdehydes. These porous organic polymers possess high Brunauer-Emmett-Teller (BET) surface areas of 995, 868, and 772 m2 g-1, respectively. Out of the three materials, TrzPOP-2 and TrzPOP-3 contain additional phenolic-OH groups along with triazine moiety and secondary amine linkages. At 273 K, TrzPOP-1, -2, and -3 displayed CO2 uptake capacities of 6.19, 7.51, and 8.54 mmol g-1, respectively, up to 1 bar pressure, which are considerably high among all porous polymers reported till date. Despite the lower BET surface area, TrzPOP-2 and TrzPOP-3 containing phenolic-OH groups showed higher CO2 uptakes. To understand the CO2 adsorption mechanism, we have further performed the quantum chemical studies to analyze noncovalent interactions between CO2 molecules and different polar functionalities present in these porous polymers. TrzPOP-1, -2, and -3 have the capability of selective CO2 uptake over that of N2 at 273 K with the selectivity of 61:1, 117:1, and 142:1 by using the initial slope comparing method, along with 108.4, 140.6, and 167.4 by using ideal adsorbed solution theory (IAST) method, respectively. On the other hand, at 298 K, the calculated CO2/N2 selectivities in the initial slope comparing method for TrzPOP-1, -2, and -3 are 27:1, 72:1, and 96:1, whereas those using IAST method are 42.1, 75.7, and 94.5, respectively. Cost effective and scalable synthesis of these porous polymeric materials reported herein for selective CO2 capture has a very promising future for environmental clean-up.

A novel class of ultra-microporous functionalized porous organic polymers (POPs) was developed starting from glyoxylic acid as a cross-linker and triflic acid as a catalyst on polyaromatic monomers, generating in situ methine bridges with carboxylic acids. This one-pot synthetic method generated functionalized POPs with high connectivity per each aromatic group and a high density of aliphatic carboxylic acids decorating the pore walls. Remarkably, the functional groups were transformed into esters, Na- and Li-carboxylates by post-synthetic modification with high yields, generating polyionic porous polymers. These porous polymers displayed excellent CO2 adsorption at 298K and isosteric heat of adsorption with values as high as 50kJ mol-1 for the Na-containing POP endowed with numerous ionic charges, as estimated by direct measurements with microcalorimetry coupled to CO2 adsorption isotherms. Dynamic breakthrough experiments on self-supporting monolithic composites demonstrated high selectivity for CO2 adsorption over N2 up to 500 for diluted streams and 340 under relevant conditions for carbon capture from flue gases (0.15 CO2 partial pressure).

Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

Constructing highly porous carbon materials from porous organic polymers for superior CO2 adsorption and separation

Optimizing bromide anchors for easy tethering of amines, nitriles and thiols in porous organic polymers towards enhanced CO2 capture

Effective functionalization of porous polymer fillers to enhance CO2/N2 separation performance of mixed-matrix membranes

As a macrocyclic host, β-cyclodextrin has a deep cavity of fixed size, as well as a unique internal hydrophobic and external hydrophilic cavity, which has excellent performance in host-guest recognition, and has been widely used in molecular recognition detection, drug delivery and other fields. Porous organic polymers have the characteristics of large specific surface area and pores, and have a good application prospect in the field of water pollution treatment.Therefore, the synthesis of β-cyclodextrin-based porous organic polymers not only has excellent host-guest recognition performance, but also has the characteristics of large specific surface area and multiple binding sites, so it has become the main design method at present. In this paper, the research status of β-cyclodextrin-based porous organic polymers in structural design and adsorption of pollutants was reviewed. The relationship between polymer structure design and adsorption performance was discussed, including adsorption of heavy metal ions and organic molecules in water. The application prospect and future development direction of β-cyclodextrin-based porous organic polymers were prospected.

Oxygen atoms have been widely used in porous organic polymers, which has attracted much attention from researchers. Herein, porous organic polymer with high oxygen content is synthesized with oxygen‐rich monomer as construction unit and anhydrous aluminum chloride as catalyst; then phase‐change materials (PCMs) composites are prepared by self‐adsorption method. The pore properties of the oxygen‐rich porous organic polymer are characterized by nitrogen absorption and desorption method. The properties of the PCM composites are characterized by scanning electron microscopy, X‐ray diffraction, Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The results show that the oxygen‐rich porous organic polymer has high Brunauer–Emmett–Teller surface area (465 m2 g−1) and excellent thermal stability. The PCM composites possess high encapsulation rate (50.6 wt%) and latent heat (124.7 kJ g−1). After several thermal cycles, the thermal properties of all PCM composites are almost unchanged, and no leakage phenomenon is found. It can be seen that oxygen‐rich porous polymers have potential applications in PCM adsorption and thermal energy storage.

Ferrocenyl Lawesson's reagent-based porous organic polymers for efficient adsorption-assisted photocatalysis degradation of organic dyes.

Porous organic polymers for superefficient removal of pollutants from water: Design, synthesis and adsorption performance

The precise control of pore structures in porous organic polymer (POP) materials is of paramount importance in addressing a wide range of challenges associated with gas separation processes. In this study, we present a novel approach to optimize the gas separation performance of POPs through the introduction of fluorine groups and figure out an important factor of reaction decision that whether the AlCl3-catalyzed polymerization is Scholl reaction or Friedel-Crafts alkylation. In the chloroform system, the steric hindrance of function groups could make direct coupling between the benzene rings difficult, which would lead to part solvent knitting (Friedel-Crafts alkylation) instead. The fluorinated polymers show enhanced surface area and pore size characteristics. Notably, the fluorinated polymers exhibited significantly improved adsorption and separation performance for SF6, as evidenced by an ideal adsorbed solution theory selectivity (SF6/N2, v: v = 50:50, 273 K) increase of 75.0, 668.8, and 502.8% compared to the nonfluorinated POPs. These findings highlight the potential of fluorination as a strategy for tailoring the properties of POP materials for advanced gas separation applications.