Synthesis Of Polymers Research Articles

Length and Sequence-Selective Polymer Synthesis Templated by a Combination of Covalent and Noncovalent Base-Pairing Interactions.

Information can be encoded and stored in sequences of monomer units organized in linear synthetic polymers. Replication of sequence information is of fundamental importance in biology; however, it represents a challenge for synthetic polymer chemistry. A combination of covalent and noncovalent base pairs has been used to achieve high-fidelity templated synthesis of synthetic polymers that encode information as a sequence of different side-chain recognition units. Dialkyne building blocks were attached to the template by using ester base pairs, and diazide building blocks were attached to the template by using H-bond base pairs. Copper-catalyzed azide-alkyne cycloaddition reactions were used to zip up the copy strand on the template, and the resulting duplex was cleaved by hydrolyzing the covalent ester base pairs. By using recognition-encoded melamine oligomers with either three phosphine oxide or three 4-nitrophenol recognition units to form the noncovalent base pairs, exceptionally high affinities of the diazides for the template were achieved, allowing the templated polymerization step to be carried out at low concentrations, which promoted on-template intramolecular reactions relative to competing intermolecular processes. Two different templates, a 7-mer and an 11-mer, were used in the three-step reaction sequence to obtain the sequence-complementary copy strands with minimal amounts of side reaction.

An Overview of Microfluidic‐assisted Strategies for Synthesis and Applications of Molecularly Imprinted Polymers

This review gives an overview of using microfluidics in conjunction with molecularly imprinted polymers (MIP), which covers two aspects: on the one hand, on‐chip synthesis of polymer and MIP particles on the nano and the micro scale. This comprises both approaches using two different immiscible solvents and homogeneous matrices to obtain the desired particle morphologies. On the other hand, especially paper‐based microfluidic systems have attracted increasing interest as low‐cost analytical tools that are inherently useful for applying at the point of care. By now, there have been several successful attempts to combine them with MIP (instead of biological recognition systems) and to successfully apply them in environmental samples, food matrices, and for diagnostic applications.

Sustainable synthesis of fine chemicals and polymers using industrial chlorine chemistry.

To achieve sustainable resource circulation, preparation of reactive species from stable compounds is unavoidable. Chlorine chemistry is an eco-friendly methodology to address this demand. Chlorine is industrially produced from sodium chloride (NaCl), an abundant natural resource in oceans. Chlorine provides various chemical products, including polymers, through chlorination and subsequent conversion reactions. In these reactions, the byproducts are usually hydrogen chloride, which is commercially utilized as hydrochloric acid and is finally neutralized to NaCl after use. Therefore, chlorine chemistry enables fine chemical production from NaCl with almost no wastage. This review provides an overview of the synthesis of fine chemicals and polymers using chlorine chemistry and discusses them from the perspective of sustainability.

Sonochemical Nitroxide-Mediated Polymerization: Harnessing Sonochemistry for Polymer Synthesis.

In polymer science, mechanochemistry is emerging as a powerful tool for materials science and molecular synthesis, offering novel avenues for controlled polymerization and post-synthetic modification. Building upon the previous research, nitroxide-mediated polymerization (NMP) is merged with mechanochemistry through the design of nitroxide-based mechanophore macroinitiators, pioneering the first instance of a sonochemical nitroxide-mediated-type polymerization. As NMP usually requires high temperatures, this study demonstrates that a sonochemical NMP-type process allows polymerization under reduced temperatures down to 55°C. Moreover, depending on the nature of the employed monomers, gelated networks are obtained, demonstrating the adaptability of the mechanophore system. This study elucidates the potential of mechanochemistry in polymer synthesis, offering insights into manipulating polymerization kinetics and advancing materials science applications.

5-Hydroxymethyl Furfural Oxidation by Perylene Diimide-Sensitized Electrodes Boosted by Photoinduced Doping.

We explored the electrochemical behavior of antimony-doped tin oxide (ATO) and perylene diimide (PDI)-sensitized ATO (ATO-PDI) for the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) mediated conversion of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a value-added substrate for alternative polymer synthesis. We first showed that ATO displayed good electrocatalytic properties towards TEMPO, affording a quasi-reversible response with a heterogeneous rate constant on the order of 2×10-4 cm s-1. We then evaluated the performance of ATO under exhaustive electrolysis of HMF in basic aqueous electrolyte, reaching 80 % Faradaic Efficiency (FE) for FDCA production. Interestingly, a significantly enhanced current (up to 2.5 mA cm-2) was recorded over time when ATO-PDI was exposed to prolonged visible illumination in a Dye-Sensitized Photoelectrochemical Cell (DSPEC) configuration, which we ascribed to the photoinduced doping of ATO resulting from the oxidative quenching of PDI excited states. The proposed system enabled the production of FDCA with ca. 75 % FE in <2 h reaction time, and an almost quantitative HMF conversion when both the mono- and di-acid products were considered. To the best of our knowledge, this is the first example of a molecular dye-sensitized interface used for the TEMPO-mediated oxidation of HMF.

Mechanistic Insights into the cis-Selective Catalytic Ring-Opening Metathesis Polymerization.

Cis-selective ring-opening metathesis polymerization (ROMP) with the commercial Grubbs "nitrato catalyst" has shown promise for synthesizing stereoregular materials, but it comes with the drawback of losing control over the molecular weight due to the poor initiation rate of the catalyst and the need for stoichiometric ruthenium complex loading. To address these issues, we developed a chain transfer polymerization method that allows for the catalytic synthesis of polymers while controlling the degree of polymerization. This allowed us to produce shorter polymers with exceptional chain-end control. Analysis of the polymers revealed a novel double monomer addition mechanism for this catalyst. MALDI-ToF mass spectrometric measurements showed that when using small monomers like norbornene, the polymer chains contained only odd numbers of monomers. In contrast, the polymerization of norbornene-imide-type monomers shows a major distribution with odd numbers of monomers along with a minor distribution of even numbers. This unique distribution of polymer chain types had not been previously observed in ROMP. We explain this phenomenon by the chiral nature of the catalyst that yields two isomeric catalytic species with dissimilar reactivities toward monomer and chain transfer agents.

Full on-device manipulation of olefin metathesis for precise manufacturing.

Olefin metathesis, as a powerful metal-catalysed carbon-carbon bond-forming method, has achieved considerable progress in recent years. However, the complexity originating from multicomponent interactions has long impeded a complete mechanistic understanding of olefin metathesis, which hampers further optimization of the reaction. Here, we clarify both productive and hidden degenerate pathways of ring-closing metathesis by focusing on one individual catalyst, using a sensitive single-molecule electrical detection platform. In addition to visualizing the full pathway, we found that the conventionally unwanted degenerate pathways have an unexpected constructive coupling effect on the productive pathway, and both types of pathway can be regulated by an external electric field. We then pushed forward this ability to ring-opening metathesis polymerization involving more interactive components. With single-monomer-insertion-event resolution, precise on-device synthesis of a single polymer was achieved by online manipulation of monomer insertion dynamics, intramolecular chain transfer, stereoregularity, degree of polymerization and block copolymerization. These results offer a comprehensive mechanistic understanding of olefin metathesis, exemplifying infinite opportunities for practical precise manufacturing.

Efficient Cross-Linking through C-H Bond Insertion of Unfunctionalized Commodity Materials Using Diazirine-Containing Polymers.

The synthesis and application of multifunctional diazirine-containing polymers for on-demand cross-linking of unfunctionalized commodity polymers through C-H bond insertion is demonstrated. While small-molecule diazirine cross-linkers have seen important applications such as plastic compatibilization and photopatterning, the high degree of functionalization of polymer-based diazirine cross-linkers offers promise for enhanced compatibility based on polymer blending and increased efficiency due to controllable multivalency. As a demonstrative example, unfunctionalized linear poly(n-butyl acrylate) (PnBA) can be cross-linked using various polymeric cross-linkers with diazirine contents as low as 0.8 wt % in 1 min under photochemical conditions. With gel fractions up to 95%, tunable rheological behavior is observed with increasing cross-linker loadings, consistent with a transition from entangled branched polymers to a cross-linked network. Moreover, the synthetic stability of the diazirine units can be exploited to prepare diazirine-containing polymers based on a variety of different backbones, from vinyl copolymers to poly(dimethylsiloxane) (PDMS), which allows successful photopatterning using a commercial 3D printer.

Synthesis of long-chain polyester polymers and their properties as crude oil pour point depressant.

Using acrylic acid advanced ester and styrene as raw materials, the long-chain polyester polymer, polyacrylic acid advanced ester-styrene pour point depressant (P-PPD), was synthesized by molecular design, and its structure was characterized by infrared spectroscopy and nuclear magnetic resonance. In addition, this study experimentally investigated the effect of P-PPD on the phase equilibrium and induction time of natural gas hydrate inhibitors in deionized water (DW) and crude oil/water (O/W) systems, respectively. Polyvinylpyrrolidone (PVP) and mono ethylene glycol (EG) were selected as representatives of kinetic hydrate inhibitor (KHIs) and thermodynamic hydrate inhibitor (THIs), respectively. The results exhibit that P-PPD played a sight role in the phase equilibrium of hydrate, while the addition of P-PPD significantly prolonged the induction time of methane hydrate both in O/W + PVP, OW + EG and O/W + PVP + EG system, indicating that the addition of as-synthesized PPD has a synergistic inhibition effect on the nucleation ability of methane hydrate and can prevent hydrate from formatting during oil and gas transport process, and thus guarantee the flow assurance. The findings of this work will provide a data reference for the hybrid use of hydrate inhibitors and pour point depressants in oil and gas transport.

Synthesis and Binding Properties of High-Affinity Histidine-Bearing Polymers for Wood Lignin.

The pursuit of molecules capable of binding to wood lignin is pivotal for advancing lignin degradation technology, particularly when combined with lignin degradation catalysts. In this study, synthetic polymers bearing histidine moieties, demonstrating remarkable affinity for wood lignin are reported. These polymers, featuring varying degrees of histidine substitution in the form of histidine methyl esters, are synthesized through controlled radical polymerization of an activated ester-bearing monomer, employing a fluorescein-labeled chain transfer agent and subsequent postpolymerization amidation with histidine methyl ester. The binding properties of these histidine-bearing polymers with milled wood lignin under aqueous conditions are investigated. Qualitative assessment of lignin-binding capabilities involve spectroscopic analysis of changes in absorbance of visible light and fluorescence intensity. Furthermore, quantitative evaluation is conducted through surface plasmon resonance measurements to determine the binding parameters of the polymers with wood lignin. Notably, polymers with higher histidine substitution exhibit enhanced binding affinity compared to those with lower histidine substitution levels.

Design of Self-Standing Chiral Covalent-Organic Framework Nanochannel Membrane for Enantioselective Sensing.

Nanochannel membranes are promising materials for enantioselective sensing. However, it is difficult to make a compromise between the selectivity and permeability in traditional nanochannel membranes. Therefore, new types of nanochannel membranes with high enantioselectivity and excellent permeability should be explored for chiral analysis. Here, asymmetric catalysis strategy is reported for interfacial polymerization synthesis of chiral covalent-organic framework (cCOF) nanochannel membrane for enantioselective sensing. Chiral phenylethylamine (S/R-PEA) and 2,4,6-triformylphloroglucinol (TP) are used to prepare chiral TP monomer. 4,4',4″-triaminotriphenylamine (TAPA) is then condensed with chiral TP to obtain cCOF nanochannel membrane via a C═N Schiff-base reaction. The molar ratio of TP to S/R-PEA is adjusted so that S/R-PEA is bound to the aldehyde only or both the aldehyde and hydroxyl groups on TP to obtain chiral-induced COF (cCOF-1) or both chiral-induced and modified COF (cCOF-2) nanochannel membrane, respectively. The prepared cCOF-2 nanochannel membrane showed two times more selectivity for limonene enantiomers than cCOF-1 nanochannel membrane. Furthermore, cCOF-2 nanochannel platform exhibited excellent sensing performance for other chiral molecules such as limonene, propanediol, methylbutyric acid, ibuprofen, and naproxen (limits of detection of 19-42ngL-1, enantiomer excess of 63.6-86.3%). This work provides a promising way to develop cCOF-based nanochannel enantioselective sensor.

Extra-framework cations promoted zeolite-encaged cobalt catalysts towards efficient ethylbenzene dehydrogenation

The transformation of ethylbenzene to styrene through direct dehydrogenation is essential process in chemical industry, indispensable for the synthesis of polymers and plastics. Herein, faujasite zeolite encaged cobalt catalyst with potassium ion as the extraframework cations, namely K-Co@Y, is reported to be a robust catalyst for ethylbenzene direct dehydrogenation, showing ethylbenzene conversion of ∼45 % and styrene selectivity of ∼95 % simultaneously under employed conditions. The superior performance of K-Co@Y in comparison with Na-Co@Y is attributed to the effective modulation of zeolite-encaged Co2+ species by extraframework K+ ions, which increases the electron density of cobalt sites and facilitates CH bond activation. Although coke deposits cause gradual deactivation, the structural integrity of K-Co@Y can be well preserved during the dehydrogenation reaction and the performance can be full restored via a simple calcination regeneration step, making K-Co@Y an eligible catalyst for long-term running in the continuous regeneration mode. This study highlights the vital role of extraframework cations in zeolite-encaged single-site catalysts for target chemical transformations and opens up a new way to modulate the performance of zeolite catalysts.

Influence of pH on the Formation of Benzyl Ester Bonds Between Dehydrogenation Polymers and Konjac Glucomannan.

A thorough understanding of the lignin-carbohydrate complex (LCC) structure has a significant meaning in the high-value utilization of lignocellulose. In this work, the complex (DHPKGC) was obtained by an addition reaction between konjac glucomannan (KGM) and quinone methides generated in the synthesis of dehydrogenation polymers (DHPs) to simulate the formation of LCCs. The effect of pH on the prepared DHPKGC was investigated. The structure of the DHPKGC was characterized by Fourier Transform Infrared (FTIR), 13C-Nuclear Magnetic Resonance (13C-NMR), and two-dimensional Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance (2D HSQC NMR) analyses. The results indicated the pH of 4.0 was conducive to the polymerization reaction between DHPs and oxidized KGM by the TEMPO/NaClO/NaBr system. In addition, the resultant DHPKGC was connected by benzyl ester linkages. Overall, this study aims to gain greater insight into the process of LCC formation in plants.

Catalyzing PET-RAFT Polymerizations Using Inherently Photoactive Zinc Myoglobin.

Protein photocatalysts provide a modular platform to access new reaction pathways and affect product outcomes, but their use in polymer synthesis is limited because co-catalysts and/or co-reductants are required to complete catalytic cycles. Herein, we report using zinc myoglobin (ZnMb), an inherently photoactive protein, to mediate photoinduced electron/energy transfer (PET) reversible addition-fragmentation chain transfer (RAFT) polymerizations. Using ZnMb as the sole reagent for catalysis, photomediated polymerizations of N,N-dimethylacrylamide in PBS were achieved with predictable molecular weights, dispersity values approaching 1.1, and high chain-end fidelity. We found that initial apparent rate constants of polymerization increased from 4.6×10-5 s-1 for zinc mesoporpyhrin IX (ZnMIX) to 6.5×10-5 s-1 when ZnMIX was incorporated into myoglobin to yield ZnMb, indicating that the protein binding site enhanced catalytic activity. Chain extension reactions comparing ZnMb-mediated RAFT polymerizations to thermally-initiated RAFT polymerizations showed minimal differences in block copolymer molecular weights and dispersities. This work enables studies to elucidate how protein modifications (e.g., secondary structure folding, site-directed mutagenesis, directed evolution) can be used to modulate polymerization outcomes (e.g., selective monomer additions towards sequence control, tacticity control, molar mass distributions).

Catalyzing PET‐RAFT Polymerizations Using Inherently Photoactive Zinc Myoglobin

AbstractProtein photocatalysts provide a modular platform to access new reaction pathways and affect product outcomes, but their use in polymer synthesis is limited because co‐catalysts and/or co‐reductants are required to complete catalytic cycles. Herein, we report using zinc myoglobin (ZnMb), an inherently photoactive protein, to mediate photoinduced electron/energy transfer (PET) reversible addition‐fragmentation chain transfer (RAFT) polymerizations. Using ZnMb as the sole reagent for catalysis, photomediated polymerizations of N,N‐dimethylacrylamide in PBS were achieved with predictable molecular weights, dispersity values approaching 1.1, and high chain‐end fidelity. We found that initial apparent rate constants of polymerization increased from 4.6×10–5 s−1 for zinc mesoporpyhrin IX (ZnMIX) to 6.5×10–5 s−1 when ZnMIX was incorporated into myoglobin to yield ZnMb, indicating that the protein binding site enhanced catalytic activity. Chain extension reactions comparing ZnMb‐mediated RAFT polymerizations to thermally‐initiated RAFT polymerizations showed minimal differences in block copolymer molecular weights and dispersities. This work enables studies to elucidate how protein modifications (e.g., secondary structure folding, site‐directed mutagenesis, directed evolution) can be used to modulate polymerization outcomes (e.g., selective monomer additions towards sequence control, tacticity control, molar mass distributions).

Mechanism of Exogenous Jasmonic Acid-Induced Resistance to Thrips palmi in Hemerocallis citrina Baroni Revealed by Combined Physiological, Biochemical and Transcriptomic Analyses

Jasmonic acid (JA) is a regulator of plant resistance to phytophagous insects, and exogenous JA treatment induces plant insect resistance. This study investigated the mechanism of exogenous JA-induced resistance of Hemerocallis citrina Baroni (daylily) to Thrips palmi at the biochemical and molecular levels. Daylily leaves sprayed with JA showed significantly higher levels of secondary metabolites—tannins, flavonoids, and total phenols, and activity of defense enzymes—peroxidase, phenylalanine ammonia lyase, polyphenol oxidase, and protease inhibitor (PI) than control leaves; the most significant effects were observed with 1 mmol L−1 JA. Owing to an improved defense system, significantly fewer T. palmi were present on the JA-treated plants than control plants. The JA-treated leaves had a smoother wax layer and fewer stomata, which was unfavorable for insect egg attachment. The differentially expressed genes (DEGs) were significantly enriched in insect resistance pathways such as lignin and wax biosynthesis, cell wall thickening, antioxidant enzyme synthesis, PI synthesis, secondary metabolite synthesis, and defense hormone signaling. A total of 466 DEGs were predicted to be transcription factors, mainly bHLH and WRKY family members. Weighted gene co-expression network analysis identified 13 key genes; TRINITY_DN16412_c0_g1 and TRINITY_DN6953_c0_g1 are associated with stomatal regulation and lipid barrier polymer synthesis, TRINITY_DN7582_c0_g1 and TRINITY_DN11770_c0_g1 regulate alkaloid synthesis, and TRINITY_DN7597_c1_g3 and TRINITY_DN1899_c0_g1 regulate salicylic acid and ethylene biosynthesis. These results indicate that JA treatment of daylily improved its resistance to T. palmi. These findings provide a scientific basis for the utilization of JA as an antagonist to control T. palmi in daylily.

Synthesis and Evaluation of High-Temperature Resistant Polymer Plugging Agent for Water-Based Drilling Fluids.

As the exploration and development of deep wells have emerged as a key option to extract more oil and gas resources trapped underneath, high-temperature formations impose stringent requirements on the thermal stability of plugging agents used in water-based drilling fluids. In this work, β-cyclodextrin, with its unique conical toroidal rigid stable structure and internal hydrophobic and external hydrophilic special adsorption capacity, was first grafted with maleic anhydride to prepare a silicone polymer and then copolymerized with dimethyldiallylammonium chloride (DMDAAC) in the presence of coupling agent vinyltriethoxysilane (A151) and cross-linking divinylbenzene (DVD) to finally obtain a high-temperature resistant plugging agent (AMMD). Subsequently, the molecular structure was evidenced and the performance of AMMD was examined in the polysulfonate-base fluid via a series of tests including high-temperature high-pressure filtration loss, sand tray plugging, and drilling fluid displacement, and the results were compared with the counterpart Soltex under the same conditions. The optimal synthesis conditions for the plugging agent were found as total monomer concentration of 25%, initiator mass fraction of 1% (based on the mass of monomers), monomer feed ratio of m (DVD):m(A151):m(DMDAAC):m(MD) of 15:3:2:15, pH value of 10, reaction temperature of 75 °C, and reaction time of 4 h. FT-IR spectra indicated that the monomers used to prepare AMMD were successfully involved in the reaction for the design of the plugging agent structure. TGA showed that AMMD has a total weight loss of about 35.98% in the range of 284 to 453 °C. Moreover, the addition of 3%AMMD into the base fluid produced a 4.38-fold and 3.8-fold filtration loss control over 60 min at 200 °C using 400 and 800 mD sand trays, respectively, which were comparatively higher than the commercially available Soltex (ca. 3.72-fold and 3.14-fold, respectively, using 400 and 800 mD). This then contributed to AMMD's superior plugging performance in drilling fluid based on the drilling fluid displacement experiment, implying that AMMD could find potential use as a plugging agent in polysulfonate drilling fluid under severe geothermal conditions.

Synthesis and optimization of 3D porous polymers for efficient CO2 capture and H2 storage

In this study, a new porous organic polymer (KFUPM-CO2) with intrinsic nitrogen atoms as active sites for CO2 capture was optimized and synthesized via Friedel-Crafts alkylation of triptycene and 2,2-bipyridine. The porous polymer shows a high surface area of 1100 m2/g with a tuned microporosity of less than 1.2 nm, confirmed by NLDFT. KFUPM-CO2 showed a remarkable CO2 sorption capacity of 5.6 mmol/g at 273 K, 3.2 mmol/g at 298 K, and a pressure of 760 mmHg KFUPM-CO2 showed a high enthalpy of adsorption of 43.7 kJ/mol for CO2 with IAST selectivity of CO2/N2 of 127 at 273 K and 97 at 298 K on simulated flue gas composition. Additionally, KFUPM-CO2 exhibited an H2 storage capacity of 1.5 wt. % at 77 K and 860 mmHg Grand Canonical Monte Carlo (GCMC) simulations further revealed that KFUPM-CO2 was mainly stabilized by π-π intra-molecular interactions, and exhibited strong van der Waals attractions to CO2 molecules via the pyridyl nitrogen atoms, resulting in the rapid uptake. The combined advantages of binding 2,2-bipyridine with triptycene provided a robust porous polymer with abundant nitrogen sites, permanent porosity, and thermal stability, rendering KFUPM-CO2 an excellent candidate for CO2 capture and H2 storage technologies.

Versatile Light‐Mediated Synthesis of Degradable Bottlebrush Polymers Using α‐Lipoic Acid

AbstractBottlebrush polymers have a variety of useful properties including a high entanglement molecular weight, low Young's modulus, and rapid kinetics for self‐assembly. However, the translation of bottlebrushes to real‐world applications is limited by complex, multi‐step synthetic pathways and polymerization reactions that rely on air‐sensitive catalysts. Additionally, most bottlebrushes are non‐degradable. Herein, we report an inexpensive, versatile, and simple approach to synthesize degradable bottlebrush polymers under mild reaction conditions. Our approach relies on the “grafting‐through” polymerization of α‐lipoic acid (LA)‐functionalized macromonomers. These macromonomers can be polymerized under mild, catalyst‐free conditions, and due to reversibility of the disulfide bond in LA, the resulting bottlebrush polymers can be depolymerized by cleaving disulfide backbone bonds. Bottlebrushes with various side‐chain chemistries can be prepared through the atom transfer radical polymerization (ATRP) of LA‐functionalized macromonomers, and the backbone length is governed by the macromonomer molecular weight and solvent polarity. We also demonstrate that LA‐functionalized macromonomers can be copolymerized with acrylates to form degradable bottlebrush networks. This work demonstrates the preparation of degradable bottlebrush polymers with a variety of side‐chain chemistries and provides insight into the light‐mediated grafting‐through polymerization of dithiolane‐functionalized macromonomers.

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.