ACS Applied Polymer Materials最新文献

{"title":"Functional Poly(p-terphenyl-co-4-acetylpyridine) Membranes for High-Temperature Proton Exchange Membrane Fuel-Cell Applications","authors":"Tian Luan,&nbsp;Yaping Jin,&nbsp;Danni Wu,&nbsp;Wei Wei,&nbsp;Jingshuai Yang* and Jin Wang*,&nbsp;","doi":"10.1021/acsapm.4c0402410.1021/acsapm.4c04024","DOIUrl":"https://doi.org/10.1021/acsapm.4c04024https://doi.org/10.1021/acsapm.4c04024","url":null,"abstract":"<p >The development of high-temperature proton exchange membranes (HT-PEMs) with low cost, simple synthetic pathways, and superior physicochemical performance is of paramount importance for their successful integration into fuel cells. Herein, we prepare HT-PEMs by grafting alkaline side-chain groups onto poly(<i>p</i>-terphenyl-<i>co</i>-4-acetylpyridine) membranes (PTAP-<i>R</i>), taking 2-chloromethylbenzimidazole (BIm) and (3-bromopropyl)trimethylammonium bromide (TAB) as functionalized reagents. Initially, PTAP is synthesized via a straightforward Friedel–Crafts polymerization process. For the purpose of increasing the phosphoric acid (PA) doping content along with improving conductivity, BIm or TAB with alkaline side chains is incorporated onto the PTAP backbones. Comparative analysis reveals that the PTAP-BIm membrane accomplishes an exceptional PA doping level of 289%, and the conductivity attains 122 mS/cm at 180 °C in nonhumidification conditions. Large amounts of PA molecules provide numerous active sites for proton transfer, leading to the development of extensive and dynamic hydrogen bonding networks along with densely interconnected transport pathways, which offer additional pathways for effective proton conduction. Furthermore, the H₂-air fuel cell utilizing PTAP-BIm membrane with 289%PA achieves a peak power density of 324 mW/cm² at 160 °C without backpressure. This study elucidates a cost-effective and mild approach for fabricating high-performance HT-PEMs that hold great potential in HT-PEM fuel-cell applications.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3224–3232 3224–3232"},"PeriodicalIF":4.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation of Epoxy-Enhanced Silica Aerogels with Thermal Insulation and Hydrophobicity by Ambient Pressure Drying","authors":"Daixuan Gong,&nbsp;Meijie Qu,&nbsp;Xincheng Wang,&nbsp;Xin Ai,&nbsp;Ping Tang,&nbsp;Wei Zhao,&nbsp;Xiaolin Wang and Yuezhen Bin*,&nbsp;","doi":"10.1021/acsapm.4c0355410.1021/acsapm.4c03554","DOIUrl":"https://doi.org/10.1021/acsapm.4c03554https://doi.org/10.1021/acsapm.4c03554","url":null,"abstract":"<p >The SiO₂ aerogel is attractive for thermal insulation but is plagued by poor mechanical and high drying process costs. Therefore, there is an urgent requirement for developing a low-cost, low-density, low-thermal conductivity, and hydrophobic monolithic SiO₂ aerogel with high strength. This work reports two epoxy-enhanced amine-modified silica aerogels (AMSA). One type is to utilize 3-aminopropyl-triethoxysilane (APTES) and tetraethylorthosilicate (TEOS) to synthesize AMSA first, ensured to be crack-free by introducing ionic liquids (IL) into the reaction system, and then cross-link with epoxy resin to obtain composite aerogels with a framework structure by a two-step enhancement gel network strategy (TES-AMSA). Composite aerogels are thermally insulating and hydrophobic, the maximum compression strength of TES-AMSA reaches 3.97 MPa, and the minimum thermal conductivity and maximum water contact angle (WCA) are 0.031 W m^–1 K^–1 and 137°, respectively. Another way is to add epoxy resin as a reinforcement to the solvent system before forming the gel network without the role of IL. A composite aerogel like the brick structure by a one-step enhancement gel network strategy (OES-AMSA) was produced under atmospheric pressure drying. The maximum compression strength of OES-AMSA reached 1.57 MPa. In addition, OES-AMSA also has a low thermal conductivity (0.035 W m^–1 K^–1) and a high WCA (143°). Two composite aerogels provide insight for the designing of pressure-resistant insulation materials, aiming to use them as an insulating material for crude oil storage tanks, ultralow-temperature refrigerators, and construction materials.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2997–3007 2997–3007"},"PeriodicalIF":4.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of a γ-Ray Protection Material with Excellent Self-Cleaning Ability","authors":"Rui Jiang,&nbsp;Xihong Xu,&nbsp;Yingchun Lu,&nbsp;Dengchao Hu,&nbsp;Yongsheng Li* and Yuanlin Zhou*,&nbsp;","doi":"10.1021/acsapm.4c0393910.1021/acsapm.4c03939","DOIUrl":"https://doi.org/10.1021/acsapm.4c03939https://doi.org/10.1021/acsapm.4c03939","url":null,"abstract":"<p >Epoxy coatings with both self-cleaning and radiation protection functions have important application prospects in the nuclear industry. However, combining these two functions poses a significant challenge. To address this challenge, epoxy resin (EP) was modified with hydroxyl-terminated polydimethylsiloxane (PDMS) as the matrix. Additionally, 1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-perfluorodecyltriethoxysilane hydrophobically modified micrometer-sized bismuth oxide (Bi₂O₃) was used as a functional filler. By adjusting the roughness with a small amount of hydrophobic silica (SiO₂), a superhydrophobic self-cleaning coating with γ radiation shielding capabilities was successfully developed. The resulting coating demonstrated exceptional self-cleaning properties, mechanical stability, and remarkable γ-ray shielding in tests.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3214–3223 3214–3223"},"PeriodicalIF":4.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Partly Sulfonated Polystyrenes Effectively Enhance the Enzymatic Saccharification of Poplar Wood under Green Liquor Pretreatment","authors":"Tian Liu,&nbsp;Peipei Wang,&nbsp;Jing Tian,&nbsp;Usama Shakeel,&nbsp;Jiaqi Guo,&nbsp;Wenyuan Zhu,&nbsp;Mohammad Rizwan Khan,&nbsp;Yongcan Jin,&nbsp;Huining Xiao and Junlong Song*,&nbsp;","doi":"10.1021/acsapm.4c0352610.1021/acsapm.4c03526","DOIUrl":"https://doi.org/10.1021/acsapm.4c03526https://doi.org/10.1021/acsapm.4c03526","url":null,"abstract":"<p >Lignosulfonate, as a water-soluble lignin, is famous for weakening the nonproductive adsorption between cellulase and substrate lignin. This study investigated the role of hydrophobic and hydrophilic components of partly sulfonated polystyrene (SPS) as lignosulfonate mimics in enhancing the enzymatic hydrolysis of lignocellulose by minimizing nonproductive cellulase–lignin interactions. SPS samples with varying molecular weights and sulfonation degrees were synthesized, the performance in enzymatic hydrolysis was evaluated, and their interactions with cellulase and lignin were analyzed. The results indicated that reducing the SPS molecular weight and degree of sulfonation significantly improved substrate enzymatic digestibility at 72 h (SED@72 h), with the optimal SPS-MW2700-61.5% enhancing SED@72 h by 20.7% and decreasing the cellulase–lignin adsorption by 81%. SPS with low sulfonation degrees spontaneously adsorbed on cellulase, driven by electrostatic interaction forces. In contrast, SPS with high sulfonation degrees adsorbed on cellulase, driven by van der Waals forces and hydrogen bonding forces. SPS formed a 1:1 complex with cellulase, preserving the enzyme activity. This research provides insights into the development of additives to minimize nonproductive adsorption during lignocellulosic enzymatic hydrolysis.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2913–2923 2913–2923"},"PeriodicalIF":4.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Perfluorocarbon-Loaded Poly(lactide-co-glycolide) Nanoparticles from Core to Crust: Multifaceted Impact of Surfactant on Particle Ultrastructure, Stiffness, and Cell Uptake","authors":"Naiara Larreina Vicente,&nbsp;Mangala Srinivas* and Oya Tagit*,&nbsp;","doi":"10.1021/acsapm.4c0336010.1021/acsapm.4c03360","DOIUrl":"https://doi.org/10.1021/acsapm.4c03360https://doi.org/10.1021/acsapm.4c03360","url":null,"abstract":"<p >Poly(lactide-<i>co</i>-glycolide) nanoparticles (PLGA NPs) loaded with Perfluoro-15-crown-5-ether (PFCE) have been developed for imaging applications. A slight modification of the formulation led to the formation of two distinct particle ultrastructures: multicore particles (MCPs) and core–shell particles (CSPs), where poly(vinyl alcohol) (PVA), a nonionic surfactant, and sodium cholate (NaCh), an anionic surfactant, were used, respectively. Despite their similar composition and colloidal characteristics, these particles have previously demonstrated significant differences in their <i>in vivo</i> distribution and clearance. We hypothesize that these differences are collectively driven by variations in their structural, chemical, and mechanical properties, which are investigated in this study. Nanomechanical characterizations of MCPs and CSPs by atomic force microscopy (AFM) revealed elastic modulus values of 54 and 270 MPa in water, respectively, indicating a better permeability and deformability of the multicore ultrastructure. The impact of the surfactant on the NP surface chemistry was evidenced by their protein corona, which was significantly greater in the CSPs. Additionally, an important amount of residual NaCh was found on the surface of CSPs, which formed strong interactions with bovine serum albumin (BSA), accounting for the difference in protein coronas and surface chemistry. Surprisingly, <i>in vitro</i> cell uptake studies showed a higher uptake of MCPs by RAW macrophages but a preference for CSPs by HeLa cells. We conclude that for this specific formulation and in this stiffness range, mechanical differences have a stronger impact in HeLa cells, while surface properties and chemical recognition play a more important role in uptake by macrophages. Overall, the extent to which a physical factor impacts cell uptake is highly dependent on the specific uptake mechanism. With this study, we provide an integrated perspective on the role of different surfactants in the particle formation process, their impact on particle ultrastructure, mechanical properties, and surface chemistry, and the overall effect on cell uptake <i>in vitro</i>.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2864–2878 2864–2878"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c03360","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D-Printable Biobased Eutectogels Based on Soybean Oil and Natural Deep Eutectic Solvents for Underwater EMG Recording","authors":"Sebastián Locatelli,&nbsp;Gisela C. Luque,&nbsp;Ruben Ruiz-Mateos Serrano,&nbsp;Antonio Dominguez-Alfaro,&nbsp;Gian Reniero,&nbsp;Matías L. Picchio,&nbsp;Joaquín Leiva,&nbsp;Luis M. Gugliotta,&nbsp;George G. Malliaras,&nbsp;David Mecerreyes,&nbsp;Ludmila I. Ronco* and Roque J. Minari,&nbsp;","doi":"10.1021/acsapm.4c0359210.1021/acsapm.4c03592","DOIUrl":"https://doi.org/10.1021/acsapm.4c03592https://doi.org/10.1021/acsapm.4c03592","url":null,"abstract":"<p >Hydrophobic eutectogels represent an emerging class of soft materials with significant potential to revolutionize underwater body signal recording and sensing technologies. Existing materials, however, are limited by poor performance or low biocompatibility. To address these challenges, herein, we propose a biobased eutectogel that combines hydrophilic and biocompatible deep eutectic solvents (DES) with a nontoxic and highly hydrophobic polymer matrix based on acrylated epoxidized soybean oil (AESO). We demonstrate fine-tuning of electrochemical, rheological, mechanical, and water-repelling properties by varying the degree of AESO functionalization and their DES composition and content. The resulting formulations demonstrated excellent suitability as inks for VAT photopolymerization three-dimensional (3D) printing, enabling the fabrication of structured hydrophobic gel electrodes. Underwater electromyography (EMG) recordings highlight the potential of these materials for use in marine biology, exploration, and environmental monitoring applications.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2945–2954 2945–2954"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Characterization of Photo-Crosslinkable Coumarin-Based Poly(lactic acid) as a Promising Material for 3D Printing Applications","authors":"Antoni Pagés-Llobet,&nbsp;Fernando Julián,&nbsp;Francesc Xavier Espinach,&nbsp;Heura Ventura,&nbsp;Helena Oliver-Ortega* and José Alberto Méndez,&nbsp;","doi":"10.1021/acsapm.5c0006710.1021/acsapm.5c00067","DOIUrl":"https://doi.org/10.1021/acsapm.5c00067https://doi.org/10.1021/acsapm.5c00067","url":null,"abstract":"<p >Poly(lactic acid) (PLA) is a biopolymer that resembles oil-based plastics in its mechanical properties. However, in manufacturing techniques such as fused deposition modeling (FDM), the inherent characteristics of the process led to a reduction in the mechanical properties of PLA-based pieces. To improve the material performance, one strategy is photo-cross-linking PLA chains. Functionalization of PLA requires grafting a molecule capable of reacting with it and ultimately cross-linking the polymeric chains. In this research, methacrylate coumarin was incorporated into PLA via free-radical grafting under reactive extrusion conditions for 5 min. The highest grafting degree value was 0.7% after the addition of 10 and 5 wt % coumarin and dicumylperoxide, respectively. Thereafter, a thin film of the material was ultraviolet (UV)-exposed for 48 h, and photo-cross-linking was confirmed with a gel formation of 16.9%. As a result, the thermal stability and melt strength of pure PLA increased by 7 °C and 1 order of magnitude, respectively. Finally, the tensile properties were evaluated by printing 3D specimens. Photo-cross-linked films were blended with nonirradiated coumarin-based PLA to obtain high infill density values (89% ± 0.8). The mechanical strength (17.8%) and stiffness (26%) of the neat PLA were enhanced.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3337–3348 3337–3348"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing Barrier Properties of Cellulose Paper: A Rosin-Based Polymer Coating Approach","authors":"Yueyue Zhu,&nbsp;Penghao Sun,&nbsp;Zhen Huang,&nbsp;He Liu* and Xu Xu*,&nbsp;","doi":"10.1021/acsapm.4c0373510.1021/acsapm.4c03735","DOIUrl":"https://doi.org/10.1021/acsapm.4c03735https://doi.org/10.1021/acsapm.4c03735","url":null,"abstract":"<p >The widespread use of plastics has caused serious environmental pollution, and the use of cellulose paper products to replace plastics has attracted worldwide attention. However, the rich hydroxyl groups and structure voids lead to poor barrier properties of cellulose paper products to water and oil. Herein, a rosin-based polymer coating (RB) is reported, which is prepared by cross-linking a rosin-modified silane coupling agent (RM) with hydroxyl-capped polydimethylsiloxane (OH-PDMS) and ethyl orthosilicate (TEOS). The RB can form a dense and uniform barrier layer on the surface of the cellulose paper product, so that the RB-coated paper (RB paper) exhibits excellent properties, including (1) water resistance (exhibiting a water contact angle of 102.3°, the relative water absorption rate decreased by over 90% at both 25 and 90 °C, reaching 35.1% and 45.9%, respectively), (2) oil resistance (Kit test reaches no. 10, and the relative oil absorption rate decreased by over 90% at both 25 and 90 °C, reaching 4.1% and 6.4%, respectively), and (3) high mechanical properties (tensile strength increased from 23.2 to 40.6 MPa, stronger than partly commercial plastics). Moreover, RB paper exhibits biodegradability and recyclability. These impressive performances position RB paper as a viable alternative to plastic.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3043–3053 3043–3053"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-Cation Doping Thermoelectric PVA Hydrogel for Self-Powered Strain Sensors","authors":"Na Tang,&nbsp;Jiayan Gong,&nbsp;Feiyang Liu,&nbsp;Jiyuan Zhang,&nbsp;Qiao Zhang*,&nbsp;ChakYin Tang,&nbsp;Gary Chi-Pong Tsui,&nbsp;Feipeng Du and Yunfei Zhang*,&nbsp;","doi":"10.1021/acsapm.5c0017710.1021/acsapm.5c00177","DOIUrl":"https://doi.org/10.1021/acsapm.5c00177https://doi.org/10.1021/acsapm.5c00177","url":null,"abstract":"<p >Recently, ionic thermoelectric hydrogels have attracted much attention, and it is desirable to use ionic thermoelectric hydrogels to couple thermoelectric properties and strain sensing performance, enabling potential applications in the field of wearable electronics. Nevertheless, simultaneously improving the Seebeck coefficient and ionic conductivity of ionic thermoelectric hydrogels remains a challenge. Here, a dual-cation doping strategy is used to regulate ion diffusion rate to improve the thermoelectric properties of ionic hydrogels, and a series of poly(vinyl alcohol) (PVA)-based hydrogels doped by dual cations (i.e., hydrogen ions and alkali metal cations, such as Li⁺, Na⁺, and K⁺) are prepared by a facile cyclic freeze–thaw method. With dual-cation doping, H⁺ and alkali metal cations interact with the hydroxyl on PVA chains, resulting in partial destruction of hydrogen bonding, which is beneficial for improving ion diffusion rate. The results show that PVA/HCl/NaCl hydrogels demonstrate a high Seebeck coefficient of 7.43 mV K^–1 and a good ionic conductivity of 33 mS cm^–1 at ambient temperature, which are much higher than those of the PVA/NaCl hydrogel. Furthermore, the PVA/HCl/NaCl ionic hydrogels exhibit good tensile strength (0.65 MPa) and sensitivity (GF = 1.25), making them suitable as flexible strain sensors to monitor body movement, with potential application in the field of wearable electronics.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3378–3388 3378–3388"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"6FDA-DAM Polyimide-Based Mixed Matrix Membranes with Functionalized UiO-67 Nanoparticles for Improved CO2 Separation Performance","authors":"Mohammad Hadi Nematollahi,&nbsp;Joaõ A. Pcoutinho,&nbsp;Reza Abedini* and Pedro J. Carvalho*,&nbsp;","doi":"10.1021/acsapm.4c0326110.1021/acsapm.4c03261","DOIUrl":"https://doi.org/10.1021/acsapm.4c03261https://doi.org/10.1021/acsapm.4c03261","url":null,"abstract":"<p >This work presents a 6FDA-DAM polyimide (PI) ((4,4′-hexafluoroisopropylidene) diphthalic anhydride 1,3,5-trimethyl-2,6-phenylenediamine) as the continuous polymeric phase for preparing mixed matrix membranes. The successful synthesis of the 6FDA-DAM polymer was verified by FTIR spectroscopy. N-heterocyclic linkers were incorporated into the UiO-67 framework, creating highly stable materials with exceptional surface areas. This enhancement improved CO₂ affinity and polymer adhesion. Field emission scanning electron microscopy images showed that the resulting films were uniformly coated with the synthesized UiO-67s, reducing the likelihood of nonselective defects in the interphase region. Gas permeation measurements demonstrated that these functionalized porous nanofillers significantly enhanced the CO₂ separation performance of the membranes. By optimizing the functionality and loading of the porous fillers, the CO₂/CH₄/N₂ separation performance was dramatically improved. Specifically, the insertion of 20 wt % of bpy25 (a mixture of biphenyl-4,4′-dicarboxylate (bpdc) and 2,2′-bipyridine-5,5′-dicarboxylic acid (bpy) in a 3:1 ratio) resulted in an exceptional CO₂ permeability of ∼1299 Barrers, a CO₂/CH₄ selectivity of ∼41.3, and a CO₂/N₂ selectivity of ∼50.7. These values are approximately 180%, 170%, and 166% higher than those of the unfilled PI. The improved separation factor is likely attributed to the abundant presence of the bipyridine moiety within the 6FDA-DAM matrix. This presence facilitates the interactions between Lewis acidic CO₂ and Lewis basic bipyridine, ultimately delivering outstanding performance that surpasses the Robeson curves for CO₂/CH₄/N₂ separations.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3008–3023 3008–3023"},"PeriodicalIF":4.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}