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Given the rapid growth of the nuclear sector, effective treatment of radioactive iodine is critical. Herein, we report the synthesis and the iodine adsorption properties of croconic acid (CTPB) and squaric acid (STPB) containing π-conjugated novel zwitterionic conjugated porous polymers (CPPs). The CPPs have been synthesized through a condensation reaction of tris(4-aminophenyl)benzene with croconic acid or squaric acid in high yields (~95%). The ionic nature of the polymers promoted high iodine/polyiodide vapour adsorption capacity of up to 4.6 g/g for CTPB and 3.5 g/g for STPB under ambient pressure at 80 °C. The zwitterionic framework (croconic acid or squaric acid units) coupled with the aromatic units is expected to effectively capture molecular iodine (I2) and polyiodides (I3- and I5-). The iodine adsorption properties of the polymers have been studied using Fourier-Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Brauner-Emmett-Teller (BET) analysis, and Raman Spectroscopy. Besides this work, there are only three ionic units for effective iodine adsorption. This work demonstrates the importance of zwitterionic units in the porous network reported for iodine adsorption and separation.

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Sensitively analyzing phenolic endocrine-disrupting chemicals (EDCs) in environmental substrates and aquatic organisms provides a significant challenge. Here, we developed a novel porous hyper-crosslinked ionic polymer bearing cyano groups (CN-HIP) as adsorbent for the highly efficient solid phase extraction (SPE) of phenolic EDCs in water and fish. The CN-HIP gave an excellent adsorption capability for targeted EDCs over a wide pH range, and the adsorption capacity was superior to that of several common commercial SPE adsorbents. The coexistence of electrostatic forces, hydrogen bond, and π-π interactions was confirmed as the main adsorption mechanism. A sensitive quantitative method was established by coupling CN-HIP based SPE method with high-performance liquid chromatography for the simultaneously determining trace bisphenol A, bisphenol F, bisphenol B and 4-tert-butylphenol in fresh water and fish. The method afforded lower detection limits (S/N = 3) (at 0.03-0.10 ng mL-1 for water and 0.8-4.0 ng g-1 for fish), high accuracy (the recovery of spiked sample at 88.0%-112 %) and high precision (the relative standard deviation < 8.5 %). This work provides a feasible method for detecting phenolic EDCs, and also opens a new perspective in developing functionalized cationic adsorbent.

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BACKGROUND: Environmental endocrine disruptors (EEDs) are a class of new pollutants that are diffusely used in the medical industry and animal husbandry. In view of toxicity concerns, elevated levels of EEDs in the environment and food, which cause potential harm to human beings and ecosystems, must be monitored. Determination of EEDs contaminants to ensure environment and food safety has became a major concern worldwide, it is also a challenging task because of their trace level and probable matrices interference. Thus, developing rapid adsorption and efficient analysis methods for EEDs is apparently necessary. RESULTS: A magnetic conjugated micro-porous polymer (Fe3O4@TbDt) was designed and synthesized, which was endowed with large specific surface area, rich functional groups and magnetic responsiveness. The material showed high extraction efficiency for EEDs via magnetic solid-phase extraction (MSPE). The quantum chemistry calculations showed the adsorption mechanism of Fe3O4@TbDt on EEDs mainly included electrostatic interactions, van der waals forces (N-H … π interaction, C-H … π interaction), and multiple hydrogen bonds. Finally, a trace analysis method for nine EEDs was established combined with HPLC-MS/MS under optimized MSPE conditions. The method showed a good linearity (R2 ≥ 0.996), low limits of detection (0.25-5.1 ng L-1), high precision (RSD of 1.1-8.2 %, n = 6). The applicability of this method was investigated by analyzing four water samples and two dairy products, and satisfactory recovery rates (82.1-100.7 %) were obtained. The proposed method showed the potential for the analysis of EEDs residues in food and environmental samples. SIGNIFICANCE: The developed MSPE method based on conjugated micro-porous polymers (CMPs) is simple, green, and efficient compared to existing techniques. The application of CMPs provides a new idea for preparing versatile sample pre-treatment materials. What's more, this work has certain reference value for addressing of EEDs residues in the environment and food.

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Charge-transfer complex formation within the pores of porous polymers is an efficient way to tune their electronical properties. Introduction of electron accepting guests to the electron donating hosts to conduct their p-doping is intensively studied in this context. However, the vice versa scenario, n-doping by treating the electron deficient (i.e., n-type) porous polymers with electron donating dopants, is rare. In this work, synthesis of an n-type phenazine based conjugated microporous polymer and its exposure to strong electron donating tetrathiafulvalene (TTF) dopants are presented. The fundamental physical characterizations (e.g., elemental analysis, gas sorption) showed that the vacuum impregnation technique is a good approach to load the guest molecules inside the pores. Moreover, the formation of charge-transfer complexes between the phenazine building blocks of the polymeric network and TTF dopants are confirmed via spectral techniques such Fourier transform infra-red, UV-vis, steady-state/time-resolved photoluminescence, and transient absorbance spectroscopies. Effect of the doping to the electronical properties is monitored by employing photoelectrochemical measurements, which showed lower charge-transfer resistivity and nearly doubled photocurrents after the doping. The study is, therefore, an important advancement for the applicability of (n-type) porous polymeric materials in the field of photo(electro)catalysis and organic electronics.

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The tunable pore walls and skeletons render covalent organic frameworks (COFs) as promising absorbents for gold (Au) ion. However, most of these COFs suffered from low surface areas hindering binding sites exposed and weak binding interaction resulting in sluggish kinetic performance. In this study, COFs have been constructed with synergistic linker and linkage for high-efficiency Au capture. The designed COFs (PYTA-PZDH-COF and PYTA-BPDH-COF) with pyrazine or bipyridine as linkers showed high surface areas of 1692 and 2076 m2 g‒1, providing high exposed surface areas for Au capture. In addition, the Lewis basic nitrogen atoms from the linkers and linkages are easily hydronium, which enabled to fast trap Au via coulomb force. The PYTA-PZDH-COF and PYTA-BPDH-COF showed maximum Au capture capacities of 2314 and 1810 mg g-1, higher than other reported COFs. More importantly, PYTA-PZDH-COF are capable of rapid adsorption kinetics with achieving 95% of maximum binding capacity in 10 min. The theoretical calculation revealed that the nitrogen atoms in linkers and linkages from both COFs are simultaneously hydronium, and then the protonated PYTA-PZDH-COF are more easily binding the AuCl4 ‒, further accelerating the binding process. This study gives the a new insight to design COFs for ion capture.

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Reactive oxygen species (ROS) play a crucial role in determining photocatalytic reaction pathways, intermediate species, and product selectivity. However, research on ROS regulation in polymer photocatalysts is still in its early stages. Herein, we successfully achieved series of modulations to the skeleton of Pyrene-alkyne-based (Tetraethynylpyrene (TEPY)) conjugated porous polymers (CPPs) by altering the linkers (1,4-dibromobenzene (BE), 4,4'-dibromobiphenyl (IP), and 3,3'-dibromobiphenyl (BP)). Experiments combined with theoretical calculations indicate that BE-TEPY exhibits a planar structure with minimal exciton binding energy, which favors exciton dissociation followed by charge transfer with adsorbed O2 to produce ⋅O2 -. Thus BE-TEPY shows optimal photocatalytic activity for phenylboronic acid oxidation and [3+2] cycloaddition. Conversely, the skeleton of BP-TEPY is significantly distorted. Its planar conjugation decreases, intersystem crossing (ISC) efficiency increases, which makes it more prone for resonance energy transfer to generate 1O2. Therefore, BP-TEPY displays best photocatalytic activity in [4+2] cycloaddition and thioanisole oxidation. Both above reactant conversion and its product selectivity exceed 99 %. This work systematically reveals the intrinsic structure-activity relationship among the skeleton structure of CPPs, excitonic behavior, and selective generation of ROS, providing new insights for the rational design of highly efficient and selective CPPs photocatalysts.

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Molecular dynamics simulations were applied to investigate the formation of P84 polyimide membranes through the non-solvent induced phase separation (NIPS) process, considering two scenarios: one using a conventional organic solvent like n-methyl-2-pyrrolidone (NMP) and the other a greener alternative, γ-butyrolactone (GBL), with water serving as the non-solvent. Different compositions of polymer solutions were established along the binodal boundaries of the respective systems, derived from experimental cloud point data on the ternary phase diagram. The resulting polymer membranes were analyzed and compared in terms of their morphology. The wettability of their surfaces was notably affected by the polymer content in the initial casting solution and demonstrated a correlation with the Brunauer-Emmet-Teller (BET) specific surface area of the associated polymer nanostructures. The GBL solvent systems produced porous polymers qualitatively similar to those obtained with NMP, albeit with slightly narrower pore size distributions.

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Structural design of 2D conjugated porous organic polymer films (2D CPOPs), by tuning linkage chemistries and pore sizes, provides great adaptability for various applications, including membrane separation. Here, four free-standing 2D CPOP films of imine- or hydrazone-linked polymers (ILP/HLP) in combination with benzene (B-ILP/HLP) and triphenylbenzene (TPB-ILP/HLP) aromatic cores are synthesized. The anisotropic disordered films, composed of polymeric layered structures, can be exfoliated into ultrathin 2D-nanosheets with layer-dependent electrical properties. The bulk CPOP films exhibit structure-dependent optical properties, triboelectric nanogenerator output, and robust mechanical properties, rivaling previously reported 2D polymers and porous materials. The exfoliation energies of the 2D CPOPs and their mechanical behavior at the molecular level are investigated using density function theory (DFT) and molecular dynamics (MD) simulations, respectively. Exploiting the structural tunability, the comparative organic solvent nanofiltration (OSN) performance of six membranes having different pore sizes and linkages to yield valuable trends in molecular weight selectivity is investigated. Interestingly, the OSN performances follow the predicted transport modeling values based on theoretical pore size calculations, signifying the existence of permanent porosity in these materials. The membranes exhibit excellent stability in organic solvents at high pressures devoid of any structural deformations, revealing their potential in practical OSN applications.

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Three-dimensional donor-acceptor (D-A) type conjugated porous polymers (CPPs) was designed and synthesized via imine condensation of copper tetraaminoporphyrin (CuTAPP) as donor and 1,3,5-tris-(4-formyl phenyl) triazine (TFPT) as acceptor, named as CuPT-CPP. The CuPT-CPP possesses a high specific surface area (73.7 m2/g) and excellent photophysical properties. The simultaneous introduction of the organometallic molecules and D-A structures in CuPT-CPP could be broadened the visible-light response range (400-800 nm) and facilitated efficient photogenerated carrier separation and transportation. As heterogeneous photocatalysts, CuPT-CPP has excellent photocatalytic performances under visible light irradiation, leading to excellent model pollutant rhodamine B degradation efficiency up to about 100% in 3 h, it has superb stability and reusability during the photocatalytic processes, and CuPT-CPP also exhibited broad substrate adaptability, which could photocatalytic degradation of methylene blue (MB), methyl orange (MO), and tetracycline hydrochloride (TC). This work indicates that three-dimensional D-A type porphyrin- and triazine-based CuPT-CPP has great potential in the practical application of photocatalysis.

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Continuous-flow syntheses using immobilized catalysts can offer efficient chemical processes with easy separation and purification. Porous polymers have gained significant interests for their applications to catalytic systems in the field of organic chemistry. The porous polymers are recognized for their large surface area, high chemical stability, facile modulation of surface chemistry, and cost-effectiveness. It is crucial to immobilize transition-metal catalysts due to their difficult separation and high toxicity. Supported phosphine ligands represent a noteworthy system for the effective immobilization of metal catalysts and modulation of catalytic properties. Researchers have been actively pursuing strategies involving phosphine-metal complexes supported on porous polymers, aiming for high activities, durabilities, selectivities, and applicability to continuous-flow systems. This review provides a concise overview of phosphine-metal complexes supported on porous polymers for continuous-flow catalytic reactions. Polymer catalysts are categorized based on pore sizes, including micro-, meso-, and macroporous polymers. The characteristics of these porous polymers are explored concerning their efficiency in immobilized catalysis and continuous-flow systems.

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Photocatalysis is an eco-friendly method to regenerate nicotinamide (NADH) cofactors, which is essential for biotransformation over oxidoreductases. Organic polymers exhibit high stability, biocompatibility and functional designability as photocatalysts, but still suffering from rapid charge recombination. Herewith the heteroatom structural engineering of donor-π-acceptor (D-π-A) conjugated porous polymers were conducted to promote charge transfer and photocatalytic NADH regeneration. The electron delocalization of polymer photocatalysts can be readily tuned by changing the electron density of the donor unit, leading to faster charge separation and better photocatalytic performance. The optimum sulfur-doped polymer exhibits the highest NADH regeneration yield of 47.4 % in 30 min and 94.1 % in 4 h, which can drive the biocatalytic C=C bond reduction of 2-cyclohexen-1-one by ene-reductase, giving the corresponding cyclohexanone yield of 96.7 % in 10 h. Moreover, the oxygen-doped polymer, from biomass derived 2,5-diformylfuran, exhibits comparable photocatalytic activity to the sulfur-doped CPP, suggesting the potential of furan as alternative donor unit to thiophene.

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Conjugated porous polymers (CPPs) are a kind of promising sensing materials for the detection of nitroaromatic compounds, but their sensing applications in aqueous media are limited because of their poor dispersity or solubility in water. In this study, we prepared anthracene and tetraphenylsilane based CPPs named PSiAn by conventional Suzuki coupling and Suzuki-miniemulsion polymerization, respectively. The structure, morphology and porosity of the CPPs were characterized by Fourier Transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), transmission electron microscope (TEM) and N2 sorption isotherm, respectively. Both of the CPPs have porous structure which is beneficial for the adsorption and diffusion of the analytes within them. The particle size of PSiAn nanoparticles prepared by Suzuki-miniemulsion polymerization is 10-40 nm from the TEM image, which facilitates the dispersion in the aqueous phase. Combined with the porosity and nanoparticle morphology, PSiAn nanoparticles realized the efficient photoluminescence (PL) sensing of nitroaromatic explosives in aqueous phase. The limit of detection (LOD) and limit of quantitation (LOQ) of PSiAn nanoparticles for 2,4,6-trinitrophenol (TNP) detection in the pure aqueous phase are 0.33 µM and 1.11 µM, respectively. Meanwhile, the good selectivity and anti-interference in presence of other nitro-compounds were observed. Furthermore, the spike/recovery test for the TNP detection in real water samples by PL sensing based on PSiAn nanoparticles indicates the quantitative recovery of TNP from 100.74 % to 101.00 %. The electrochemical test, ultraviolet-visible absorption spectra, excitation and emission spectra, and time-resolved PL spectra were investigated to explore the PL sensing mechanism. As a result, it is found that the fluorescence inner filter effect might be the predominant quenching mechanism during the detection of nitrophenolic compounds such as TNP and 4-nitrophenol (4-NP).

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Since the invention of the triboelectric nanogenerator (TENG), porous polymer materials (PPMs), with different geometries and topologies, have been utilized to enhance the output performance and expand the functionality of TENGs. In this review, the basic characteristics and preparation methods of various PPMs are introduced, along with their applications in TENGs on the basis of their roles as electrodes, triboelectric surfaces, and structural materials. According to the pore size and dimensionality, various types of TENGs that are built with hydrogels, aerogels, foams, and fibrous media are classified and their advantages and disadvantages are analyzed. To deepen the understanding of the future development trend, their intelligent and multifunctional applications in human-machine interfaces, smart wearable devices, and self-powering sensors are introduced. Finally, the future directions and challenges of PPMs in TENGs are explored to provide possible guidance on PPMs in various TENG-based intelligent devices and systems.

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High internal phase emulsion (HIPE) templating is a well-established method for the generation of polymeric materials with high porosity (>74%) and degree of interconnectivity. The porosity and pore size can be altered by adjusting parameters during emulsification, which affects the properties of the resulting porous structure. However, there remain challenges for the fabrication of polyHIPEs, including typically small pore sizes (∼20-50 µm) and the use of surfactants, which can limit their use in biological applications. Here, we present the use of gelatin, a natural polymer, during the formation of polyHIPE structures, through the use of two biodegradable polymers, polycaprolactone-methacrylate (PCL-M) and polyglycerol sebacate-methacrylate (PGS-M). When gelatin is used as the internal phase, it is capable of stabilising emulsions without the need for an additional surfactant. Furthermore, by changing the concentration of gelatin within the internal phase, the pore size of the resulting polyHIPE can be tuned. 5% gelatin solution resulted in the largest mean pore size, increasing from 53 µm to 80 µm and 28 µm to 94 µm for PCL-M and PGS-M respectively. In addition, the inclusion of gelatin further increased the mechanical properties of the polyHIPEs and increased the period an emulsion could be stored before polymerisation. Our results demonstrate the potential to use gelatin for the fabrication of surfactant-free polyHIPEs with macroporous structures, with potential applications in tissue engineering, environmental and agricultural industries.

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In this article, newly designed 3D porous polymers with tuned porosity were synthesized by the polycondensation of tetrakis (4-aminophenyl) methane with pyrrole to form M1 polymer and with phenazine to form M2 polymer. The polymerization reaction used p-formaldehyde as a linker and nitric acid as a catalyst. The newly designed 3D porous polymers showed permanent porosity with a BET surface area of 575 m2/g for M1 and 389 m2/g for M2. The structure and thermal stability were investigated by solid 13C-NMR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). The performance of the synthesized polymers toward CO2 and H2 was evaluated, demonstrating adsorption capacities of 1.85 mmol/g and 2.10 mmol/g for CO2 by M1 and M2, respectively. The importance of the synthesized polymers lies in their selectivity for CO2 capture, with CO2/N2 selectivity of 43 and 51 for M1 and M2, respectively. M1 and M2 polymers showed their capability for hydrogen storage with a capacity of 66 cm3/g (0.6 wt%) and 87 cm3/g (0.8 wt%), respectively, at 1 bar and 77 K. Molecular dynamics (MD) simulations using the grand canonical Monte Carlo (GCMC) method revealed the presence of considerable microporosity on M2, making it highly selective to CO2. The exceptional removal capabilities, combined with the high thermal stability and microporosity, enable M2 to be a potential material for flue gas purification and hydrogen storage.

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Although skin-like sensors that can simultaneously detect various physical stimuli are of fair importance in cutting-edge human-machine interaction, robotic, and healthcare applications, they still face challenges in facile, scalable, and cost-effective production using conventional active materials. The emerging two-dimensional transition metal carbide, Ti3C2Tx MXene, integrated with favorable thermoelectric properties, metallic-like conductivity, and a hydrophilic surface, is promising for solving these problems. Herein, skin-like multifunctional sensors are designed to precisely detect and distinguish temperature and pressure stimuli without cross-talk by decorating elastic and porous substrates with MXene sheets. Because the combination of the thermoelectric and conductive MXene with the thermally insulating, elastic, and porous substrate integrates efficient Seebeck and piezoresistive effects, the resultant sensor exhibits not only an ultralow detection limit (0.05 K), high signal-to-noise ratio, and excellent cycling stability for temperature detection but also high sensitivity, fast response time, and outstanding durability for pressure detection. Based on the impressive dual-mode sensing properties and independent temperature and pressure detections, a multimode input terminal and an electronic skin are created, exhibiting great potential in robotic and human-machine interaction applications. This work provides a scalable fabrication of multifunctional tactile sensors for precisely detecting and distinguishing temperature and pressure stimuli.

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Three novel N-rich hypercrosslinked porous polymers (NHCP1, NHCP2, and NHCP3) were facilely developed using Friedel-Crafts alkylation. NHCP1 with a remarkably large surface area (2066 m2 g-1) showed the best adsorption performance for chlorophenol pollutants. A sensitive and simple method was developed by using NHCP1 as a sorbent for solid-phase extraction to preconcentrate several chlorophenols in honey, water, and peach beverage samples followed by determination using a high-performance liquid chromatography-ultraviolet detector. The detection wavelength was 280 nm. Under the optimized conditions, the linear ranges were 1.67-1000 ng g-1 for honey, 0.170-100 ng mL-1 for water, and 0.330-100 ng mL-1 for peach beverage samples. The detection limits (S/N = 3) were 0.500-2.00 ng g-1, 0.0500-0.100 ng mL-1, and 0.100-0.200 ng mL-1, respectively. Recovery values were 89.3-111% with relative standard deviations <9.4%. The proposed extraction/preconcentration and quantitative analysis method provides an affordable and effective alternative for the preconcentration and determination of low levels of chlorophenols in real samples.

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An increasing number of high-performing gas separation membranes is reported almost on a daily basis, yet only a few of them have reached commercialisation while the rest are still considered pure research outcomes. This is often attributable to a rapid change in the performance of these separation systems over a relatively short time. A common approach to address this issue is the development of mixed matrix membranes (MMMs). These hybrid systems typically utilise either crystalline or amorphous additives, so-called fillers, which are incorporated into polymeric membranes at different loadings, with the aim to improve and stabilise the final gas separation performance. After a general introduction to the most relevant models to describe the transport properties in MMMs, this review intends to investigate and discuss the main advantages and disadvantages derived from the inclusion of fillers of different morphologies. Particular emphasis will be given to the study of the compatibility at the interface between the filler and the matrix created by the two different classes of additives, the inorganic and crystalline fillers vs. their organic and amorphous counterparts. It will conclude with a brief summary of the main findings.

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Life on earth is dependent on clean water, which is crucial for survival. Water supplies are getting contaminated due to the growing human population and its associated industrialization, urbanization, and chemically improved agriculture. Currently, a large number of people struggle to find clean drinking water, a problem that is particularly serious in developing countries. To meet the enormous demand of clean water around the world, there is an urgent need of advanced technologies and materials that are affordable, easy to use, thermally efficient, portable, environmentally benign, and chemically durable. Physical, chemical and biological methods are used to eliminate insoluble materials and soluble pollutants from wastewater. In addition to cost, each treatment carries its limitations in terms of effectiveness, productivity, environmental effect, sludge generation, pre-treatment demands, operating difficulties, and the creation of potentially hazardous byproducts. To overcome the problems of traditional methods, porous polymers have distinguished themselves as practical and efficient materials for the treatment of wastewater because of their distinctive characteristics such as large surface area, chemical versatility, biodegradability, and biocompatibility. This study overviews improvement in manufacturing methods and the sustainable usage of porous polymers for wastewater treatment and explicitly discusses the efficiency of advanced porous polymeric materials for the removal of emerging pollutants viz. pesticides, dyes, and pharmaceuticals whereby adsorption and photocatalytic degradation are considered to be among the most promising methods for their effective removal. Porous polymers are considered excellent adsorbents for the mitigation of these pollutants as they are cost-effective and have greater porosities to facilitate penetration and adhesion of pollutants, thus enhance their adsorption functionality. Appropriately functionalized porous polymers can offer the potential to eliminate hazardous chemicals and making water useful for a variety of purposes thus, numerous types of porous polymers have been selected, discussed and compared especially in terms of their efficiencies against specific pollutants. The study also sheds light on numerous challenges faced by porous polymers in the removal of contaminants, their solutions and some associated toxicity issues.

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3D printing technology has been used to directly produce various actual products, ranging from engines and medicines to toys, especially due to its advantage in producing items of complicated, porous structures, which are inherently difficult to clean. Here, we apply micro-/nano-bubble technology to the removal of oil contaminants from 3D-printed polymeric products. Micro-/nano-bubbles show promise in the enhancement of cleaning performance with or without ultrasound, which is attributed to their large specific surface area enhancing the adhesion sites of contaminants, and their high Zeta potential which attracts contaminant particles. Additionally, bubbles produce tiny jets and shock waves at their rupture, driven by coupled ultrasound, which can remove sticky contaminants from 3D-printed products. As an effective, efficient, and environmentally friendly cleaning method, micro-/nano-bubbles can be used in a range of applications.