Nanoporous Organic Polymers Research Articles

Room-Temperature Synthesis of a Fluorine-Functionalized Nanoporous Organic Polymer for Highly Efficient SF6 Adsorption and Separation.

Sulfur hexafluoride (SF6) is widely used in the power industry and significantly contributes to the greenhouse effect, necessitating the development of efficient materials for SF6 capture, particularly fluorine-containing materials. However, existing fluorine-containing materials often require complex monomers and high synthesis temperatures. Herein, we report the synthesis of a fluorine-functionalized carbazole-based nanoporous organic polymer (CNOP-7) at room temperature, using commercially available 4,4'-bis(9H-carbazole-9-yl)-1,1'-biphenyl and 1,1,1-trifluoroacetone. CNOP-7 contains 14.7% fluorine atoms and exhibits a high specific surface area of 1270 m2·g-1, demonstrating excellent SF6 adsorption and separation performance. The SF6/N2 selectivity of CNOP-7 reaches 107 at 273 K and 73 at 298 K. Furthermore, dynamic breakthrough experiments confirm that CNOP-7 can efficiently and repeatedly separate SF6 from SF6/N2 mixtures. Molecular simulations reveal the mechanism behind its efficient separation. This work offers fresh perspectives on the development and fabrication of adsorbents for efficient SF6 sequestration.

Facilely Incorporating Photoresponsive Triphenylamine into a Robust Nanoporous Organic Polymer by Click Reaction for Photocatalytic Oxidation Reactions

Facilely Incorporating Photoresponsive Triphenylamine into a Robust Nanoporous Organic Polymer by Click Reaction for Photocatalytic Oxidation Reactions

Highly Selective SO2 Capture by Triazine-Functionalized Triphenylamine-Based Nanoporous Organic Polymers.

The emissions of sulfur dioxide (SO2) from combustion exhaust gases pose significant risks to public health and the environment due to their harmful effects. Therefore, the development of highly efficient adsorbent polymers capable of capturing SO2 with high capacity and selectivity has emerged as a critical challenge in recent years. However, existing polymers often exhibit poor SO2/CO2 and SO2/N2 selectivity. Herein, we report two triazine-functionalized triphenylamine-based nanoporous organic polymers (ANOP-6 and ANOP-7) that demonstrate both good SO2 uptake and high SO2/CO2 and SO2/N2 selectivity. These polymers were synthesized through cost-effective Friedel-Crafts reactions using cyanuric chloride, 3,6-diphenylaminecarbazole, and 2,2',7,7'-tetrakis(diphenylamino)-9,9'-spirobifluorene. The resultant ANOPs are composed of triazine and triphenylamine units and feature an ultramicroporous structure. Remarkably, ANOPs exhibit impressive adsorption capacities for SO2, with uptakes of approximately 3.31-3.72 mmol·g-1 at 0.1 bar, increasing to 9.52-9.94 mmol·g-1 at 1 bar. The static adsorption isotherms effectively illustrate the ability of ANOPs to separate SO2 from SO2/CO2 and SO2/N2 mixtures. At 298 K and 1 bar, ANOP-6 shows outstanding selectivity toward SO2/CO2 (248) and SO2/N2 (13146), surpassing all previously reported triazine-based nanoporous organic polymers. Additionally, dynamic breakthrough tests demonstrate the superior separation properties of ANOPs for SO2 from an SO2/CO2/N2 mixture. ANOPs exhibit a breakthrough time of 73.1 min·g-1 and a saturated SO2 capacity of 0.53 mmol·g-1. These results highlight the exceptional adsorption properties of ANOPs for SO2, indicating their promising potential for the highly efficient capture of SO2 from flue gas.

Highly selective separation of sulfur dioxide in a triphenylamine-based nanoporous organic polymer

The urgent need for effective SO2 capture materials has driven research into the development of novel nanoporous organic polymers (NOPs). Herein, we developed a triphenylamine-based nanoporous organic polymer, designated as ANOP-5, through the self-condensation of an AB2 triphenylamine monomer. The adsorption/separation properties of SO2 and CO2 are comparatively evaluated through the investigation of static gas adsorption isotherms. At 273 K and 100 kPa, ANOP-5 displays a high SO2 adsorption capacity of 399 cm3 g−1 and a high selectivity of 388 for SO2/CO2, with a molar ratio of SO2 to CO2 at 10/90. The exceptional performance of desulfurization is attributed to the strong interaction between ANOP-5 and SO2, in addition to the ultramicroporous structure. These findings are further supported by the dispersion-corrected density functional theory calculations. This study contributes valuable insights into the design and preparation of NOPs with high gas adsorption properties, particularly for addressing environmental pollution challenges related to SO2 emissions.

Exploring Nanomaterials for Hydrogen Storage: Advances, Challenges, and Perspectives.

Hydrogen energy heralded for its environmentally friendly, renewable, efficient, and cost-effective attributes, stands poised as the primary alternative to fossil fuels in the future. Despite its great potential, the low volumetric density presents a formidable challenge in hydrogen storage. Addressing this challenge necessitates exploring effective storage techniques for a sustainable hydrogen economy. Solid-state hydrogen storage in nanomaterials (physically or chemically) holds promise for achieving large-scale hydrogen storage applications. Such approaches offer benefits, including safety, compactness, lightness, reversibility, and efficient generation of pure hydrogen fuel under mild conditions. This article presents solid-state nanomaterials, specifically nanoporous carbons (activated carbon, carbon fibers), metal-organic frameworks, covalently connected frameworks, nanoporous organic polymers, and nanoscale metal hydrides. Furthermore, new developments in hydrogen fuel cell technology for stationary and mobile applications have been demonstrated. The review outlines significant advancements thus far, identifies key barriers to practical implementation, and presents a perspective for future sustainable energy research. It concludes with recommendations to enhance hydrogen storage performance for cost-effective and long-lasting utilization.

A nanoporous organic polymer using 1, 3-dibromoadamantane as a crosslinker for adsorption/separation of benzene and cyclohexane.

The development of nanoporous organic polymers with cycloaliphatic components for effective benzene (Bz) and cyclohexane (Cy) adsorption/separation poses a significant challenge. This work focuses on synthesizing NOP-Ad-1, a nanoporous organic polymer derived from a Friedel-Crafts reaction between cycloaliphatic 1,3-dibromadantane and aromatic hexaphenylbenzene. At 298 K and P/P0 = 0.95, NOP-Ad-1 can uptake 989 mg g-1 benzene and 441 mg g-1 cyclohexane. Moreover, as the benzene vapor ratio increased from 20% to 80%, the Bz/Cy selectivity of NOP-Ad-1 gradually decreased from 1.75 to 1.24. These findings highlight the potential application of NOP-Ad-1 in the adsorption/separation of Bz/Cy mixtures.

Synthesis of triphenylamine-based nanoporous organic polymers for highly efficient capture of SO2 and CO2

Two triphenylamine-based nanoporous organic polymers were synthesized through the self-condensation of AB2 monomers. These polymers exhibit promising potential for capturing toxic gases and contaminants due to their highly effective uptake of SO2.

Structurally Locked Xanthene Dye-Stitched Nanoporous Organic Polymers for Efficient Photooxidative Reactions

Structurally Locked Xanthene Dye-Stitched Nanoporous Organic Polymers for Efficient Photooxidative Reactions

Synthesis of a Carbazole-Based Nanoporous Organic Polymer for Efficient Adsorption/Separation of C2H2 and CO2

Synthesis of a Carbazole-Based Nanoporous Organic Polymer for Efficient Adsorption/Separation of C₂H₂ and CO₂

Construction of a Carbazole-Based Nanoporous Organic Polymer via an AB2 Monomer for Adsorption/Separation of C1–C3 Alkanes and CO2

Construction of a Carbazole-Based Nanoporous Organic Polymer via an AB₂ Monomer for Adsorption/Separation of C₁–C₃ Alkanes and CO₂

Natural Ellagic Acid-Derived Nanoporous Organic Polymers for CO2 and Organic Dye Adsorption

The utilization of natural renewable molecules to fabricate functional materials is of great significance. In this work, two bioinspired porous organic polymers (POPs), namely, EA-TAPB and EA-TAPT, were easily prepared from ellagic acid (EA) and C3-symmetric amines via an aqueous diazo-coupling strategy. Both azo-linked POPs exhibit good stability and possess a hierarchical nanoporous structure with abundant neighboring phenol groups. Benefiting from these, the as-prepared POPs showed excellent performances in the selective capture of CO2 and in the charge-selective adsorption of dyes. Particularly, the superhydrophilicity of EA groups in these azo-linked POPs renders them with ultrafast removal ability of cationic dyes from water. The pseudo-second-order constants of EA-TAPB are 47.314 and 12.300 g mg–1 min–1 for MB and RhB, respectively, which are superior to those reported adsorption materials. This work represents an effective approach to constructing low-cost functional POPs for task-specific applications.

Design of hydroxyl-functionalized nanoporous organic polymer with tunable hydrophilic-hydrophobic surface for solid phase extraction of neonicotinoid insecticides.

As being widely used insecticides, neonicotinoid residues are toxic and harmful to human health and aquatic ecosystems. Thus, the sensitive monitoring of neonicotinoids in water and food samples is highly desirable to reduce their risks to humans. Herein, four novel hydroxyl-functionalized nanoporous organic frameworks (OH-NOP1, OH-NOP2, OH-NOP3 and OH-NOP4) with tunable hydrophilic-hydrophobic surface have been designed and fabricated for the first time by employing luteolin as monomer and 4,4'-bis(chloromethyl)-1,1'-biphenyl as crosslinker at the molar ratio of 3:1, 1:1, 1:3 and 1:6, respectively. When the molar ratio of luteolin to crosslinker was 1:3, OH-NOP3 was obtained and it presented the highest affinity with excellent adsorption performance towards the studied neonicotinoids. The adsorption mechanism was proposed to be the strong hydrogen bond, polar interaction, Lewis acid-base interaction and pore adsorption between OH-NOP3 and neonicotinoids. Then, utilizing OH-NOP3 as sorbent for solid phase extraction cartridges, an effective method for extraction and preconcentration of neonicotinoids followed by high performance liquid chromatography analysis has been developed for quantitative detection of neonicotinoids from water and edible fungi. The method provided good linearity over the range of 0.06-100.0ngmL-1 for lake water, 1.5-100.0ngg-1 for pleurotus eryngii and sea-shroom. Low detection limit (at the signal to noise ratio of 3) was achieved in the range of 0.02-0.08ngmL-1 for water, 0.50-0.60ngg-1 for pleurotus eryngii and 0.50-0.80ngg-1 for sea-shroom, while the limit of quantification was 0.06-0.25ngmL-1, 1.50-1.80ngg-1 and 1.50-2.50ngg-1, respectively. Satisfactory method recoveries (85.1-112%) were obtained, with relative standard deviations below 8.2%. This study offered a new strategy for designing efficient sorbents to adsorb or remove organic pollutants based on the structure and properties of substrates.

Highly efficient separation of C1-C3 alkanes and CO2 in carbazole-based nanoporous organic polymers

The rational design and preparation of nanoporous organic polymers (NOPs) with high-efficiency separation of natural gas remains challenging. Two carbazole-based NOPs, CNOP-3 and CNOP-4, are prepared via a facile Friedel-Crafts (FC) hydroxyalkylation reaction using inexpensive carbazole and tetrakis(4-aldehydephenyl)methane (TFPM) and 1,3,5,7-tetrakis(4′-aldehydephenyl)adamantane (TFPAd), respectively. The surface areas and pore size of spherical particles CNOPs range from 769 m2/g and 0.52 nm to 1007 m2/g and 1.14 nm, respectively. Additionally, the porosity parameters of the polymers, interactions between the gases and the polymer skeleton, and the physicochemical parameters of gases (e.g., polarizabilities, critical temperatures, molecular sizes) strongly influence the adsorption behaviors of light hydrocarbons, including propane (C3H8), ethane (C2H6), and methane (CH4). In addition, the CNOPs with high nanoporosity and rich polar N–H group demonstrated a significant adsorption of CO2 (72.3–83.4 cm3·g−1) at 273 K/100 kPa. Notably, at 298 K/100 kPa, the adsorption selectivities of C3H8/CH4, C2H6/CH4, CO2/CH4, and C3H8/C2H6 also reach 370, 25.3, 8.1, and 10.3, respectively, outperforming the previously reported nanoporous materials. These results indicate that the as-synthesized CNOPs derived from tetrahedral geometry building blocks and carbazole can efficiently separate C3H8, C2H6, CO2, and CH4 from natural gas under ambient conditions.

Versatile Nanoporous Organic Polymer Catalyst for the Size-Selective Suzuki–Miyaura Coupling Reaction

Heterogenous catalysts with confined nanoporous catalytic sites are shown to have high activity and size selectivity. A solution-processable nanoporous organic polymer (1-BPy-Pd) catalyst displays high catalytic performance (TON > 200K) in the heterogeneous Suzuki–Miyaura coupling (SMC) reaction and can be used for the preparation of the intermediates in the synthesis of pharmaceutical agents. In comparison to the homogeneous catalyst analogue (2,2′-BPy)PdCl2, the heterogenous system offers size-dependent catalytic activity when bulkier substrates are used. Furthermore, the catalyst can be used to create catalytic impellers that simplify its use and recovery. We found that this system also works for applications in heterogenous Heck and nitroarenes reduction reactions. The metal-binding nanoporous polymer reported here represents a versatile platform for size-selective heterogeneous and recyclable catalysts.

Friedel–Crafts Synthesis of Carbazole-Based Hierarchical Nanoporous Organic Polymers for Adsorption of Ethane, Carbon Dioxide, and Methane

Friedel–Crafts Synthesis of Carbazole-Based Hierarchical Nanoporous Organic Polymers for Adsorption of Ethane, Carbon Dioxide, and Methane

Facile Preparation of Triphenylamine-Based Nanoporous Organic Polymers for Adsorption/Separation of C1–C3 Hydrocarbons and CO2 in Natural Gas

The development of porous organic polymers with high gas adsorption and separation performances by a facile preparation process has progressively addressed the urgent demand for cost-effective adsorbents employed in energy-efficient purification and recovery processes. However, these polymeric materials are still poorly developed for the practical adsorption and separation of light C1–C3 hydrocarbon components, such as methane (CH4), ethane (C2H6), and propane (C3H8), from natural gas under ambient conditions. The present work addresses this issue by reporting the facile preparation of two triphenylamine-based nanoporous organic polymers (ANOPs), ANOP-M and ANOP-A, via acid-catalyzed Friedel–Crafts hydroxyalkylation polymerization using commercially available triphenylamine with tetrakis(4-formylphenyl)methane and 1,3,5,7-tetrakis(4′-formylphenyl)adamantane monomers, respectively. The specific surface areas of the ANOPs vary from 1052 to 1272 m2/g, with average pore sizes of 1.36 nm. Furthermore, the ANOP networks are demonstrated to be highly interconnected. Interestingly, the ANOPs have different adsorption capacities toward different C1–C3 hydrocarbons (CH4, C2H6, and C3H8) and CO2 molecules, and ANOP-M shows the highest uptake of C3H8 (97.9 cm3/g) and C2H6 (64.6 cm3/g) among these gas molecules at 298 K and 1 bar. Analyses reveal that these differences depend greatly upon the physical parameters of the gas molecules (e.g., polarizability, critical temperature, and molecular size) and the porosity parameters of the ANOPs, as well as the affinity between the gases and the polymer skeleton. The adsorption selectivities of the ANOPs in conjunction with C3H8/CH4, C2H6/CH4, C3H8/C2H6, C3H8/CO2, C2H6/CO2, and CO2/CH4 gas mixtures also differ significantly and exhibit values of 151–164, 17.5–17.8, 6.16–6.43, 14.2–15.1, 2.93–3.17, and 4.35–4.70, respectively. Accordingly, the facile preparation and excellent light hydrocarbon adsorption and separation properties of the ANOPs make these materials highly promising for applications involving the adsorption/separation of C1–C3 light hydrocarbons and CO2 from natural gas under ambient conditions.

Facile Preparation of Cost‐Effective Triphenylamine‐Based Nanoporous Organic Polymers for CO2, I2, and Organic Solvents Capture

AbstractSeeking cost‐effective construction of nanoporous organic polymers for CO2 and I2 capture and organic solvents adsorption remains challenging. Two triphenylamine‐based nanoporous organic polymers, ANOP‐1 and ANOP‐2, have been prepared successfully by Friedel–Crafts (F–C) hydroxyalkylation from low‐cost triphenylamine (TPA) with commercial terephthalaldehyde and isophthalaldehyde, respectively. The effect of isomers of phenyl dialdehydes on the structure of porous architecture is investigated. The as‐prepared ANOPs exhibit a moderate uptake of CO2, I2, and organic solvents because of the electron‐rich TPA unit and nanometer‐scale pore size of <2 nm. These findings demonstrate that F–C hydroxyalkylation is a cost‐effective strategy for producing large amounts of triphenylamine‐enriched, high specific BET surface area materials to develop commercial organic materials for industrial use.

Synthesis of the Magnetically Nanoporous Organic Polymer Fe3O4@SiO2-NH2-COP and Its Application in the Determination of Sulfonamide Residues in Surface Water Surrounding a Cattle Farm.

Efficient extractions of trace antibiotic residues in the environment are a key factor for accurate quantification of the residues. A new nanoporous material, namely, magnetically covalent organic polymer (MCOP, Fe3O4@SiO2-NH2-COP) was synthesized in this work and was used for magnetic solid-phase extraction (MSPE). The combination of MSPE with high-performance liquid chromatography separation together with ultraviolet detection (HPLC-UV) was established as an effective method for the determination of four sulfonamide (SA) residues in surface water surrounding a cattle farm. The synthesized magnetic material was characterized by SEM, TEM, FT-IR, magnetic properties measurement system (MPMS), and nitrogen gas porosimetry. The material possessed many attractive features, such as a unique microporous structure, a larger specific surface area (137.93 m2·g−1) than bare Fe3O4 (24.84 m2·g−1), high saturation magnetization (50.5 emu·g−1), open adsorption sites, and high stability. The influencing parameters, including pH, the used amount of MCOPs, the type of eluent, adsorption solution, and desorption time, were optimized. Under the optimized conditions, the method conferred good linearity ranges (R2 ≥ 0.9990), low detection limits (S/N = 3, LOD, 0.10–0.25 μg·L−1), and satisfactory recoveries (79.7% to 92.2%). The enrichment factor (EF) for the four SAs was 34.13–38.86. The relative standard deviations of intraday (n = 5) and of interday (n = 3) were less than 4.8% and 8.9%, respectively. The equilibria between extraction and desorption for SAs could be reached within 150 s. The proposed method was sensitive and convenient for detecting SA residues in complex environmental matrices, and the successful application of the new MCOPs as an adsorbent was demonstrated.

Synthesis of natural proanthocyanidin based novel magnetic nanoporous organic polymer as advanced sorbent for neonicotinoid insecticides

In this work, a natural proanthocyanidin (PA) based magnetic nanoporous organic polymer (named as PA-MOP) was successfully synthesized for the first time. The PA-MOP possessed high hydrophilic-surface, good magnetic responsiveness and high affinity for neonicotinoid insecticides. It was applied as an advanced magnetic sorbent for extraction of four neonicotinoids (thiamethoxam, imidacloprid, acetamiprid and thiacloprid) from environmental water, peach juice and honey samples prior to HPLC analysis. Under optimal conditions, the limits of detection for the analytes at S/N = 3 were 0.02–0.08 ng mL−1 for water, 0.03–0.10 ng mL−1 for peach juice and 0.05–0.16 ng g−1 for honey sample. The method recoveries were 80.0%-114.8%, with the relative standard deviations below 6.8%. The values of matrix effect were from −1.5% to −9.3%. Based on theory calculation, the extraction mechanism can be attributed to multiple interactions between the PA-MOP and the neonicotinoids, in which hydrogen bonding, π-π stacking and electrostatic interactions are the major interactions.

Porphyrin-Based Nanoporous Organic Polymers for Adsorption of Carbon Dioxide, Ethane, and Methane

Porphyrin-Based Nanoporous Organic Polymers for Adsorption of Carbon Dioxide, Ethane, and Methane