Porous Organic Polymers Research Articles

Porous organic polymers from cashew nut shell liquid: Derived carbonized material for carbon dioxide capture

AbstractThe fast developing world is in search of measures to control the accumulation of unused by‐products and waste materials generated during the production of useful commodities. Accordingly, wastes from agro‐industrial sectors can form raw materials for the production of various resources that are extensively used in many areas such as gas sorption and energy production. In the present work, cashew nut shell liquid (CNSL), the vesicant liquid present in the outer shell of cashew seed, forms the source material for the synthesis of porous organic polymers for carbon dioxide capture. Herein, novel types of hypercrosslinked polymers (HCPs) are synthesized via a simple Friedel–Crafts reaction with CNSL as the starting material. Polymerization of natural CNSL with dimethoxymethane/bis‐(chloromethyl)‐biphenyl as external crosslinker provides products in quantitative yield. One of the synthesized HCP is tuned to attain the required high porosity by carbonization at elevated temperatures using an activator. Thus, activated carbon material prepared at 700°C is found to have a high surface area of 880 m2/g with a good carbon dioxide adsorption capacity of 14.72 wt%. These porous materials had moderate isosteric heat of adsorption (23–31 kJ/mol) with excellent recycling capability.

A Nickel-Doped Dehydrobenzoannulene-Based Porous Organic Polymer for the Catalytic Desulfurization of Dibenzothiophenes and Benzothiophenes

A Nickel-Doped Dehydrobenzoannulene-Based Porous Organic Polymer for the Catalytic Desulfurization of Dibenzothiophenes and Benzothiophenes

Palladium-anchored calix[4]arene-derived porous organic polymer towards efficient hydrolytic cleavage of carbon disulfide

The release of carbon disulfide can have adverse effects on our environment and human health. The stability of carbon disulfide and the slow kinetics of hydrolysis can make it challenging to achieve efficient and practical cleavage of the CS bonds. Herein, a calix[4]arene-based porous organic polymer (CPOP-1) is innovatively synthesized through an optimized polycondensation reaction using C-Methylcalix[4]resorcinarene and hexafluoro-hexaazatriphenylene as monomers. Subsequently, palladium-induced calix[4]arene-based porous organic polymer was also synthesized via strong Pd−N coordination bonds to construct the metal-induced porous catalyst (CPOP-2). The polymeric catalyst active center [Pd2+(N^N)(NO3-)2] demonstrated outstanding catalytic hydrolysis performance (11.14 μmol g-1 h-1) in 10.5 h which is significantly enhanced by ca.13.2 times as compared to reported mononuclear Bpy-Pd(NO3)2, and 7.07 times than model trinuclear complex catalyst HATN-Pd-1, respectively. The control experiments revealed that POP catalysts showcased robust stability, prolonged effectiveness, and feasible recyclability during the hydrolytic cleavage of carbon disulfide at room temperature in aqueous solutions. Furthermore, the coordination environment of [Pd2+(N^N)] was validated through XPS, EXAFS, and isotope labeling measurements, and the hydrolysis cleavage products were confirmed e. g. CO2, sulfide, and protons. More importantly, a reaction mechanism was formulated coupled with theoretical calculations, and simulations. The proposed mechanism involves sequential OH- nucleophilic attacks on the carbon atoms of insert-coordinated CS2 and COS, leading to the cleavage of double CS bonds and the formation of CO bonds. The concurrent dissociation of the C−S bond and liberation of CO2 result in an intermediate structure characterized by [(N^N)Pd2+](SH-)2. This intermediate motif serves as the source of the thermodynamic driving force for the reaction.

Organic cage-based frameworks: from synthesis to applications

The investigation of organic cage-based frameworks (OCFs) has attracted increasing attention over the past decade due to their versatile synthetic methods and broad property range resulting from the unique combination of porous organic cages (POCs) with diverse framework materials, including porous organic polymers (POPs), metal-organic frameworks (MOFs), and supramolecular organic frameworks (SOFs). Nevertheless, a comprehensive summary of the research advancements in OCFs remains elusive in the literature. This review addresses this gap by providing a detailed overview of the development of OCF-based materials from both synthetic and applicative perspectives. The discussion begins with systematically exploring design principles and common strategies for elaborating OCFs, achieved by rational selection of bond-forming routes suitable for various POC monomers, including covalent bonds, coordination bonds, and supramolecular interactions. Subsequently, the review highlights the functional attributes derived from the distinctive structural features of OCFs, showcasing their task-specific applications in adsorption/separation, catalysis, membrane technology, and other fields. Lastly, the article summarizes the opportunities and challenges anticipated as the exploration of the OCF family continues to advance in material science.

Amide-Based Porous Organic Polymers for Efficient Loading of Photosensitizers and Production of Reactive Oxygen Species for Antimicrobial Applications

Amide-Based Porous Organic Polymers for Efficient Loading of Photosensitizers and Production of Reactive Oxygen Species for Antimicrobial Applications

Optimizing Adsorption‐Redox Sites and Charge Transfer of Ternary Polymer Photocatalyst with P─N Linkage for CO2 Conversion Coupled with Antibiotics Removal

AbstractThe rational design of bifunctional photocatalysts with high adsorption and enrichment characteristics and excellent photocatalytic redox activity is an effective way to address environmental pollution and energy shortage crisis. In this study, cyclophosphazene‐derived porous organic polymer (PCPD) microspheres with P─N linkage are coated with graphene oxide (GO) and loaded with Ag0 nanoparticles (NPs) to prepare covalently bonded xAg‐rGO/PCPD composites. The catalyst with the highest specific surface area (denoted as 2.5Ag‐rGO/PCPD) shows excellent adsorption capacity for fluoroquinolone antibiotics, removing 96.2% of ciprofloxacin (CIP) through adsorption. By applying the catalyst with the best photocatalytic redox activity (denoted as 5Ag‐rGO/PCPD), 82.97% of refractory sulfonamide antibiotics are removed through adsorption‐degradation, and 635.3 µmol g−1 of CO and 162.3 µmol g−1 of CH4 are generated as products of CO2 photoreduction alone. Among the co‐catalytic systems, the highest CO yield of 9.16 µmol g−1 is obtained by coupling CO2 reduction with levofloxacin (LVX) degradation to harness the electron‐donating power of the pollutant molecule. This study is expected to provide useful guidance for the rational design of bifunctional photocatalysts.

Recent advances in research on sample pretreatment methods based on supramolecular-derived porous organic polymers

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.

Mild and friendly preparation of a high-surface porous organic polymers and its application for sensitive detections of endocrine disrupting chemicals

For sample pretreatment technique, the preparation of a stable, practical material with excellent enrichment performance is the core, and especially the preparation of an environmentally friendly adsorbent is desired. The preparation of most materials involves the use of organic solvents, which puts a strain on the environment to a certain extent, and the choice of aqueous solution as the reaction environment for the diazo-coupling reaction has attracted great attention, as a friendly strategy. We prepared the environmentally friendly porous organic polymer (POP) 2,4,6-tris(2,4,6-trihydroxyphenyl)-1,3,5-triazine-4,4′-diaminobiphenyl (CTT-BD) by diazo-coupling reaction, and further fabricated as stable solid phase microextraction (SPME) fiber. It achieved efficient extraction of derivatized bisphenol endocrine disrupting chemicals (EDCs) from water samples with enrichment factors ranging from 1306 to 2781. Under the optimum experimental conditions, the developed method by combining the CTT-BD coated fiber with gas chromatography mass spectrometry (GC–MS), demonstrated a wide linearity (10–10000 ng/L), low limits of detection (2.0–3.0 ng/L) and good reproducibility (relative standard deviations 3.1–8.1 %). Finally, the proposed method has been successfully used for the determinations of EDCs from water samples, and satisfactory recoveries (85.6–118.0 %) were achieved.

Recent Advances in Porous Bio-Polymer Composites for the Remediation of Organic Pollutants.

The increasing awareness of the importance of a clean and sustainable environment, coupled with the rapid growth of both population and technology, has instilled in people a strong inclination to address the issue of wastewater treatment. This global concern has prompted individuals to prioritize the proper management and purification of wastewater. Organic pollutants are very persistent and due to their destructive effects, it is necessary to remove them from wastewater. In the last decade, porous organic polymers (POPs) have garnered interest among researchers due to their effectiveness in removing various types of pollutants. Porous biopolymers seem to be suitable candidates among POPs. Sustainable consumption and environmental protection, as well as reducing the consumption of toxic chemicals, are the advantages of using biopolymers in the preparation of effective composites to remove pollutants. Composites containing porous biopolymers, like other POPs, can remove various pollutants through absorption, membrane filtration, or oxidative and photocatalytic effects. Although composites based on porous biopolymers shown relatively good performance in removing pollutants, their insufficient strength limits their performance. On the other hand, in comparison with other POPs, including covalent organic frameworks, they have weaker performance. Therefore, porous organic biopolymers are generally used in composites with other compounds. Therefore, it seems necessary to research the performance of these composites and investigate the reasons for using composite components. This review exhaustively investigates the recent progress in the use of composites containing porous biopolymers in the removal of organic pollutants in the form of adsorbents, membranes, catalysts, etc. Information regarding the mechanism, composite functionality, and the reasons for using each component in the construction of composites are discussed. The following provides a vision of future opportunities for the preparation of porous composites from biopolymers.

Phosphate-based, heteroatom-rich porous organic polymers for efficacious uptake of iodine in vapor phase

Radioactive iodine pollution from nuclear waste poses significant threat to both the environment and human health. As a result, the utmost importance lies in the capture and safe storage of radioactive iodine. To address this concern, a set of porous organic polymers with phosphate linkages, namely AZO-POP-P, OPN-3, OPN-4, and OPN-5, were synthesized for the uptake of iodine in vapor phase. Additionally, a triazine-based porous organic polymer, AZO-POP-T was also synthesized to compare the iodine uptake capacity. Syntheses of these phosphate-linked and triazine-based polymers involved a nucleophilic substitution reaction of various aromatic alcohols with POCl3 or cyanuric chloride, respectively. This study represents an inaugural investigation into the iodine uptake capability by phosphate-based porous organic polymers. They exhibited efficient iodine capture from vapor phase, demonstrating uptake capacities of 3.56, 1.30, 2.70, and 0.63 g.g−1 for AZO-POP-P, OPN-3, OPN-4, and OPN-5 respectively, at 75 °C. Meanwhile, the triazine-based AZO-POP-T exhibited an uptake capacity of 1.83 g.g−1 at 75 °C. These porous organic polymers demonstrated easy and scalable synthesis, high thermal stability, and recyclability for at least five cycles without significant decrease in the uptake capacity towards volatile iodine from vapour phase.

Porous Organic Polymers for Efficient and Selective SO2 Capture from CO2‐rich Flue Gas

AbstractThe quest for effective technologies to reduce SO2 pollution is crucial due to its adverse effects on the environment and human health. Markedly, removing a ppm level of SO2 from CO2‐containing waste gas is a persistent challenge, and current technologies suffer from low SO2/CO2 selectivity and energy‐intensive regeneration processes. Here using the molecular building blocks approach and theoretical calculation, we constructed two porous organic polymers (POPs) encompassing pocket‐like structures with exposed imidazole groups, promoting preferential interactions with SO2 from CO2‐containing streams. Markedly, the evaluated POPs offer outstanding SO2/CO2 selectivity, high SO2 capacity, and an easy regeneration process, making it one of the best materials for SO2 capture. To gain better structural insights into the notable SO2 selectivity of the POPs, we used dynamic nuclear polarization NMR spectroscopy (DNP) and molecular modelling to probe the interactions between SO2 and POP adsorbents. The newly developed materials are poised to offer an energy‐efficient and environment‐friendly SO2 separation process while we are obliged to use fossil fuels for our energy needs.

Porous Organic Polymers for Efficient and Selective SO2 Capture from CO2-rich Flue Gas.

The quest for effective technologies to reduce SO2 pollution is crucial due to its adverse effects on the environment and human health. Markedly, removing a ppm level of SO2 from CO2-containing waste gas is a persistent challenge, and current technologies suffer from low SO2/CO2 selectivity and energy-intensive regeneration processes. Here using the molecular building blocks approach and theoretical calculation, we constructed two porous organic polymers (POPs) encompassing pocket-like structures with exposed imidazole groups, promoting preferential interactions with SO2 from CO2-containing streams. Markedly, the evaluated POPs offer outstanding SO2/CO2 selectivity, high SO2 capacity, and an easy regeneration process, making it one of the best materials for SO2 capture. To gain better structural insights into the notable SO2 selectivity of the POPs, we used dynamic nuclear polarization NMR spectroscopy (DNP) and molecular modelling to probe the interactions between SO2 and POP adsorbents. The newly developed materials are poised to offer an energy-efficient and environment-friendly SO2 separation process while we are obliged to use fossil fuels for our energy needs.

Polyaniline-Based Cationic Porous Organic Polymers for Fast and Efficient Anion-Exchange-Driven Capture of Cr2O7 2.

Efficient treatment of wastewater contaminated with carcinogenic Cr(VI) has been a long-term challenge for both academic and industrial research efforts. Removal of Cr(VI) species by ion exchange is a relatively simple and efficient method, and its combination with highly tailorable nanomaterials is promising for the treatment of such wastewater. Here, we report a type of cationic porous organic polymer (POP), namely, PTPA-PIP, which can be prepared simply by converting the corresponding aromatic polyamine PTPA to its protonated form, thereby significantly increasing its hydrophilicity and ability to disperse homogeneously in water, crucial for application in water treatment. In addition to detailed characterization of the physicochemical properties of PTPA-PIP (including using Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), and solid-state NMR techniques), adsorption experiments demonstrate that PTPA-PIP removes low-concentration dichromate anions with very high performance, including excellent exchange capacity (maximum capacity of 230 mg Cr2O7 2-/g PTPA-PIP), ultrafast removal (initial adsorption rate of 83 mg g-1 min-1), excellent selectivity (∼10% loss of adsorption capacity in the presence of 40-fold concentration of competing anions), as well as superior reusability (reusable for at least 5 cycles without compromised performance). These results demonstrate that PTPA-PIP is an outstanding candidate for application in industrial settings for the effective removal of harmful Cr(VI) pollutants in wastewater.

Bidirectionally regulated synthetic ferrocene-based aminal-linked porous organic polymer artificial enzyme towards photothermal-amplified synergistic antibacterial and wound healing therapy

Development of hetero-atom rich porous organic polymers (POPs) in facile and easy accessible methods are of significant importance to broad application potentials and enrich diversity of such materials. Here, a bidirectional adjustment strategy, starting with amino and aldehyde monomers, concurrently, was used for the rational preparation of N-rich aminal-linked POPs with customized structure and function. Five novel ferrocene-based aminal-linked POPs, were facilely fabricated via the one-pot catalyst-free Schiff base polycondensation between the 1,1′-Ferrocene dicarboxaldehyde and different types of triazine-bearing monomers with diverse geometrical features and functions (Porphyrin, cationic viologen, Ferrocene, 1,4,7,10-tetraazacyclododecane, and benzyl). The concurrent introduction of Ferrocene (redox-active) and triazine-Porphyrin (photoactive) endowed remarkable mimicking peroxidase-like activity and excellent photothermal and photodynamic activity with Fc-TDPP, which could be used as a broad spectrum fungicide, exerting photothermal enhanced photodynamic and enzyme antibacterial therapy. Notably, in vitro and in vivo experiments confirmed Fc-TDPP could not only kill S. aureus and E. coli quickly and efficiently, but also significantly accelerate the repairing of open wounds with S. aureus-infection. The as-proposed strategy are available for the low-cost constructing N-rich POPs with specific structure and functions targeted for wide potential applications in various fields.

Ionic Porous Organic Polymer as a Visible-Light Photocatalyst: Efficient Heterogeneous Oxidation of Arylmethylene Compounds and Alcohols Using Molecular Oxygen

Ionic Porous Organic Polymer as a Visible-Light Photocatalyst: Efficient Heterogeneous Oxidation of Arylmethylene Compounds and Alcohols Using Molecular Oxygen

Facile Synthesis of a Multifunctional Porous Organic Polymer Nanosonosensitizer (mHM@HMME) for Enhanced Cancer Sonodynamic Therapy.

Sonodynamic therapy (SDT), which involves the activation of sonosensitizers to generate cytotoxic reactive oxygen species under ultrasound irradiation, is a promising noninvasive modality for cancer treatment. However, the clinical translational application of SDT is impeded by the lack of efficient sonosensitizers, the inefficient accumulation of sonosensitizers at tumor sites, and the complicated immunosuppressive tumor microenvironment. Herein, we developed a facilely synthesized multifunctional porous organic polymer nanosonosensitizer (mHM@HMME) for enhanced SDT. Specifically, mHM@HMME nanosonosensitizers were prepared by incorporating chemotherapeutic mitoxantrone into the one-step synthesis process of disulfide bond containing porous organic polymers, followed by loading with organic sonosensitizer (HMME) and camouflaging with a cancer cell membrane. Due to the cancer cell membrane camouflage, this multifunctional mHM@HMME nanosonosensitizer showed prolonged blood circulation and tumor targeting aggregation. Under ultrasound irradiation, the mHM@HMME nanosonosensitizer exhibited a satisfactory SDT performance both in vitro and in vivo. Moreover, the potent SDT combined with glutathione-responsive drug release in tumor cells induced robust immunogenic cell death to enhance the antitumor effect of SDT in turn. Overall, this facilely synthesized multifunctional mHM@HMME nanosonosensitizer shows great potential application in enhanced SDT.

Carbon Dioxide Capture by Emerging Innovative Polymers: Status and Perspectives.

A significant amount of research has been conducted in carbon dioxide (CO2) capture, particularly over the past decade, and continues to evolve. This review presents the most recent advancements in synthetic methodologies and CO2 capture capabilities of diverse polymer-based substances, which includes the amine-based polymers, porous organic polymers, and polymeric membranes, covering publications in the last 5 years (2019-2024). It aims to assist researchers with new insights and approaches to develop innovative polymer-based materials with improved capturing CO2 capacity, efficiency, sustainability, and cost-effective, thereby addressing the current obstacles in carbon capture and storage to sooner meeting the net-zero CO2 emission target.

Resistive Memristors Using Robust Electropolymerized Porous Organic Polymer Films as Switchable Materials.

Porous organic polymers (POPs) with inherent porosity, tunable pore environment, and semiconductive property are ideally suitable for application in various advanced semiconductor-related devices. However, owing to the lack of processability, POPs are usually prepared in powder forms, which limits their application in advanced devices. Herein, we demonstrate an example of information storage application of POPs with film form prepared by an electrochemical method. The growth process of the electropolymerized films in accordance with the Volmer-Weber model was proposed by observation of atomic force microscopy. Given the mechanism of the electron transfer system, we verified and mainly emphasized the importance of porosity and interfacial properties of porous polymer films for memristor. As expected, the as-fabricated memristors exhibit good performance on low turn-on voltage (0.65 ± 0.10 V), reliable data storage, and high on/off current ratio (104). This work offers inspiration for applying POPs in the form of electropolymerized films in various advanced semiconductor-related devices.

Superlative Porous Organic Polymers for Photochemical and Electrochemical CO2 Reduction Applications: From Synthesis to Functionality.

To mimic the carbon cycle at a kinetically rapid pace, the sustainable conversion of omnipresent CO2 to value-added chemical feedstock and hydrocarbon fuels implies a remarkable prototype for utilizing released CO2. Porous organic polymers (POPs) have been recognized as remarkable catalytic systems for achieving large-scale applicability in energy-driven processes. POPs offer mesoporous characteristics, higher surface area, and superior optoelectronic properties that lead to their relatively advanced activity and selectivity for CO2 conversion. In comparison to the metal organic frameworks, POPs exhibit an enhanced tendency toward membrane formation, which governs their excellent stability with regard to remarkable ultrathinness and tailored pore channels. The structural ascendancy of POPs can be effectively utilized to develop cost-effective catalytic supports for energy conversion processes to leapfrog over conventional noble metal catalysts that have nonlinear techno-economic equilibrium. Herein, we precisely surveyed the functionality of POPs from scratch, classified it, and provided a critical commentary of its current methodological advancements and photo/electrochemical achievements in the CO2 reduction reaction.

Electrochemical sensing of Pb2+, Cu2+, and Hg2+ by an aminoclay-based porous covalent organic polymer/ multi-walled carbon nanotubes modified glassy carbon electrode

We present a novel electrochemical sensor for the simultaneous detection of Lead (Pb2+), Copper (Cu2+), and Mercury (Hg2+) ions in seafood samples using differential pulse anodic stripping voltammetry (DPASV) technique. The sensor incorporates an aminoclay-based porous covalent organic polymer (AC-PCOP) derived from the polymerization of aminoclay and 1,3,5-benzenetricarboxylic acid (trimesic acid). To enhance conductivity, the AC-PCOP is combined with multi-walled carbon nanotubes (MWCNTs) and utilized for modifying the surface of the glassy carbon electrode (GCE). The AC-PCOP was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, and infrared spectroscopy (IR). These analyses confirmed the presence of a hierarchical architecture in the AC-PCOP, which exhibited a spherical shape. The proposed modifier facilitates the deposition-stripping process and electron diffusion between electrolyte and heavy metal ions. Optimized conditions yielded limit of detections (LODs) of 0.0006, 0.0016, and 0.0003 nM, with linear ranges from 0.002 to 1000 nM, 0.005 to 1000 nM, and 0.001 to 1000 nM for Pb2+, Cu2+, and Hg2+, respectively. The sensor successfully measured these ions in seafood samples. Control experiments and validation were performed using cold vapor atomic absorption spectrometry (CVAAS) to determine the ions in the chosen food samples.