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PIM-1
JOURNAL OF APPLIED POLYMER SCIENCE · 2024 · IF 2.7

Carboxylated PIM-1 incorporating sulfonated graphene oxide effectively improves the ion transport properties of the membrane

Yuanhang Song,Tao Wang,Jingxian Zhang,Yanhui Li,Junru Li,Chuanwei Zhang,Pengfei Zhang

This study explores the ion transport properties of self-microporous polymers by introducing a novel combination of carboxylated PIM-1 with sulfonated graphene oxide (SGO) to fabricate membranes. The resulting membranes exhibit enhanced structural stability, hydrophilicity, and ion exchange capacity (IEC) compared with the original carboxylated PIM-1 (CPIM-1), while preserving the subnanoporous structure. However, it was observed that excessive SGO loading leads to a detrimental “blocking effect” that compromises various membrane properties. Through electrically driven ion transport tests in a 0.01 M NaCl solution, it is demonstrated that a moderate amount of SGO effectively enhances membrane conductivity from 46.96 μS m −1 (for carboxylated PIM-1 membranes without SGO) to 56.55 μS m −1 . Additionally, the membranes exhibit selective sieving of cations and anions. The presence of small-sized ion channels and the electrostatic repulsion generated by the abundant carboxyl and sulfonic acid groups significantly hinder Cl − transport. Consequently, the Na + /Cl − migration ratio (t + /t − ) reaches 98 at a concentration ratio of 10:1 on both sides of the membrane, surpassing the value of 3.74 observed for the pure CPIM-1 membrane. This investigation provides valuable insights for the practical application of easily prepared, processable, and cost-effective hydrophilic self-contained microporous polymer membranes in ion transport applications.

研究领域: 材料科学 · 化学工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2020 · IF 3.573

PIM-1/PAN Thin-Film Composite Hollow Fiber Membrane as Structured Packings for Isopropanol (IPA)/Water Distillation

Xu Zhang,Rui Hou,Jun Zhang,Qin Meng,Chong Shen,Guoliang Zhang

In this study, novel polymers of intrinsic microporosity (PIMs)-based hollow fiber structured packings were prepared by a facile pour-coating method and successfully applied as structured packings for isopropanol (IPA)/water distillation. The design of an ultrathin PIM-1 layer on the inner surface of hollow fibers effectively protected the membrane from mechanical damage, especially when assembled into the module. Based on the material properties and specific polymer chain structures, the hydrophobic PIM-1 layer made composite membranes to not only have a strong affinity for alcohols and moisture resistance but also possess a large surface area and excellent stability, which effectively decreased the membrane resistance and promoted the fast membrane transfer rate during the distillation process. The prepared PIM-1/PAN hollow fiber structured packings with a controllable defect-free PIM-1 layer down to 34 nm can be easily operated far beyond the normal flooding limit and achieve a very low height of a mass transfer unit (HTU) of 4.0 cm.

研究领域: 化学工程 · 材料科学
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POLYMER · 2024 · IF 4.1

PIM-1-assisted structuring of amine-functionalized porous organic copolymer for post-combustion carbon dioxide capture

Xuelin Zhang,Shuangqi Song,Jingde Li,Yanqin Yang

Capturing CO 2 from flue gas of coal-burned power plants has been considered to be a promising technology to mitigate the environmental problems caused by rising level of CO 2 at the atmosphere. Amine-functionalized adsorbents, showing impressive CO 2 adsorption capability and selectivity even at low CO 2 partial pressure, face the challenge of permanent structural changes and performance deterioration due to the irreversibly bonding of SO 2 , a common impurity of flue gas, particularly under humid condition. Besides, the reported amine-functionalized adsorbents are usually nano-sized powders, impractical for industrial applications. Therefore, the development of efficient, stable, and structured CO 2 adsorbents is still an urgent need. Herein, we develop a novel structured mixed-matrix adsorbent (PIM-PP-DETA), using a diethylenediamine-appended porous organic copolymer (PP-DETA, prepared by a copolymerization reaction of dichloro- p -xylene and 4,4′-bis(chloromethyl)biphenyl and a one-step amine grafting process) as main adsorbent and PIM-1 as polymer matrix through a phase inversion process. The as-developed PIM-PP-DETA not only exhibits high CO 2 adsorption capacity and outstanding CO 2 selectivity over N 2 , but also shows fast adsorption kinetics and high stability under repeated adsorption-desorption cycling under dynamic flow conditions. Furthermore, PIM-PP-DETA possesses high tolerance towards acidic and moist environments, with CO 2 adsorption capacity remained at a relatively high level after SO 2 and humid exposure, suggesting its potential usage to post-combustion CO 2 capture.

研究领域: 材料科学 · 环境科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2020 · IF 5.774

Metal-organic framework MOF-801/PIM-1 mixed-matrix membranes for enhanced CO2/N2 separation performance

Wenbo Chen,Zhenguo Zhang,Lei Hou,Cancan Yang,Hongcheng Shen,Kai Yang,Zhe Wang

This work mainly studies the CO 2 separation performance of a new type mixed-matrix membranes (MMMs) based on MOF-801 as the microporous filler and PIM-1 as the polymer matrix. MMMs was successfully formed via simple casting/solvent evaporation approach at room temperature. The samples were systematically characterized by SEM, XRD, TGA and FTIR, the permeability-selectivity of MMMs to CO 2 , O 2 and N 2 was studied by gas permeability test. The experimental results show that the uniform dispersion of the CO 2 -philic MOF-801 filler provides a channel for the rapid and selective transport of CO 2 , so the MOF-801/PIM-1 MMMs revealed much higher CO 2 permeability and CO 2 /N 2 ideal selectivity (CO 2  = 9686 Barrer, CO 2 /N 2  = 27, all selectivity in the paper is ideal) than pure polymer membrane. After 90-days aging test, the CO 2 permeability of MMMs remains above 70%, which reflects its good anti-aging performance. After 120 h continuous gas permeability test, it also shows good long-term working stability. The experimental results show that the good gas separation performance of MMMs   exceeds the Robeson upper bound (2008), showing good application prospect for practical greenhouse gas CO 2 separation.

研究领域: 材料科学 · 环境科学
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ACS Applied Polymer Materials · 2024 · IF 4.4

Surface-Modified Sodalite (SOD) Zeolite and Preparation of Mixed Matrix Membranes with Polymers of Intrinsic Microporosity (PIM-1) for Efficient Gas Separation

Shuai Han,Junjian Yu,Fei Wang,Xiangwei Li,Hongzhe Ni,Yuchao Wang,Zhe Wang

Zeolite is a commonly utilized filler in mixed matrix membranes (MMMs) to enhance the effectiveness of gas separation due to its molecular sieving properties with high separation coefficients. However, the compatibility and suitability between the zeolite and the polymer membrane are prerequisites for preparing homogeneous membranes and an essential factor affecting gas separation performance. Herein, we synthesized nucleus-crown-crown structures by surface modification of SOD zeolite and prepared MMMs by doping them into Polymers of Intrinsic Microporosity (PIM-1) for efficient gas separation. FTIR, XRD, SEM, and TGA characterized the fillers and the MMMs. The average particle size of the filler was estimated to be approximately 552.43 nm by SEM images. The surface-modified SOD zeolite facilitates the rapid permeation of specific gas molecules and enhances the dispersion of SOD zeolite in the PIM-1 membrane, thereby improving gas separation performance. Compared with pure PIM-1 membrane, the MMMs with a loading of 7 wt % exhibited CO2 and H2 permeabilities reaching up to 7000.0 and 3600.0 Barrer; their selectivities for CO2/N2 and H2/N2 were measured at 17.7 and 9.29, respectively. MMMs with the best fill ratios exceeded the 2008 Robeson upper limits. The methods for surface modification of SOD zeolites provide a new way for the application of SOD zeolite in the area of gas separation.

研究领域: 材料科学 · 化学工程
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ChemistrySelect · 2024 ·Vol. 9 ·期 11 ·e202400114 · IF 1.9

Blended Membrane of Polyethylene-Glycol-Grafted-PIM-1 and Tröger's Base Polymer for the Separation of Pentose and Hexose

Jin Liang,Xiaoxin Wang,Dongsheng Yu,XiTao Luo,Xiangfeng Liang,Zhongliang Su,Qinghui Shou

Graphical Self-supported osmotic membranes were prepared by blending PIM-1-mPEG, which was obtained by modifying PIM-1 with polyethylene glycol monomethyl ether (mPEG), and hydrophilic Tröger's base polymer (DMBP-TB). The membranes utilized microporous molecular sieves and the differences in solute-membrane interactions to achieve high pentose/hexose selectivity in aqueous solutions. Monosaccharides are vital building blocks in bioengineering applications; however, their extraction from intricate mixtures is challenging and uses substantial amounts of energy. Polymers of intrinsic microporosity (PIMs) offer an innovative avenue for separating monosaccharides. We modified PIM-1membranes to improve the glucose/xylose separation by incorporating polyethylene glycol monomethyl ether (mPEG). The optimal mPEG (molecular weight: 1000 Da; mass fraction: 2.5 %; solvent: methanol) delivered a xylose separation coefficient of 2.62. With the hybrid membrane of PIM-1-mPEG (50 w.t.%) and hydrophilic Tröger's base polymerer (DMBP-TB, 50 w.t.%), the separation factor for xylose/glucose in an aqueous solution was 2.51 for single-stage running and 11.32 after five-stage running. There are large fractions of micropores for PIM-1-mPEG, and there is difference on solute-membrane interactions for pentose/hexose, which are regarded to be the main driving force for the high pentose/hexose selectivity in methanol. The blending of PIM-1-mPEG and DMBP-TB, integrates the microporosity and hydrophilicity, finally endues the high pentose/hexose selectivity in aqueous solution. These microporous membranes are promising materials for efficiently separating monosaccharides and jnl> small organic molecules while minimizing energy consumption. We established a solid foundation for further exploring microporous membranes for various applications, notably in bioengineering.

研究领域: 生物工程 · 材料科学 · 分离技术
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JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

PIM-1 mixed matrix membranes incorporated with magnetic responsive cobalt-based ionic liquid for O2/N2 separation

Hongyong Zhao,Ting Song,Xiaoli Ding,Ruyi Cai,Xiaoyao Tan,Yuzhong Zhang

Membrane technology for O 2 /N 2 separation is a mature industrial unit. Membranes with excellent permeation-separation performance are still one of the critical requirements. The cobalt-based compounds have been well known for their good affinity for O 2 , which can facilitate O 2 transfer and improve the O 2 /N 2 selectivity in membranes. The cobalt-based compounds, moreover, have a magnetic responsive effect, which can lead to a further improvement in O 2 /N 2 separation under a magnetic field. A class of PIM-1 mixed matrix membranes (MMMs), containing cobalt-based ionic liquid (CILs)@polyarylate (aromatic polyester) (PAR) (core-shell) composite nanospheres (CILs@PAR (c-s) CNPs), were prepared. Chemical compositions of CILs@PAR (core-shell) CNPs were determined by Fourier transform infrared spectroscopy (FTIR). Morphologies and structures of CILs@PAR (core-shell) CNPs were observed by transmission electron microscopy (TEM). Gas adsorption properties of CILs@PAR (core-shell) CNPs were tested. Thermal properties of the (CILs@PAR (c-s) CNPs)/PIM MMMs were investigated by simultaneous thermal analysis (TGA-DSC). Gas permeation-separation performances of the (CILs@PAR (c-s) CNPs)/PIM MMMs were also reported. Compared with the original PIM-1 membrane, the (CILs@PAR (c-s) CNPs)/PIM MMMs display higher O 2 /N 2 selectivity because of cobalt-based ionic liquid as O 2 carrier, coupled with a reduction in O 2 permeability. With increasing the content of the CILs@PAR (c-s) CNPs, the O 2 /N 2 selectivity increases, and the O 2 permeability decreases. It is also found that, as a magnetic field on the MMMs, the O 2 /N 2 selectivity further increases; and it increases more, as a higher content of CILs@PAR (c-s) CNPs. Therefore, the (CILs@PAR (c-s) CNPs)/PIM MMMs exhibit excellent O 2 /N 2 selectivity of ∼5 coupled with good O 2 permeability of ∼140 Barrer under a 180 mT magnetic field and show great potential for air separation.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 化学工程 · 分离技术
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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Interfacial Property Modulation of PIM-1 through Polydopamine-Derived Submicrospheres for Enhanced CO2/N2 Separation Performance

Guanying Dong,Jingjing Zhang,Zheng Wang,Jing Wang,Peixia Zhao,Xingzhong Cao,Yatao Zhang

Polydopamine-modified additives have been thus far widely used in the mixed matrix membranes (MMMs) for gas separation. However, very few reports focus on the polydopamine alone and investigate its contribution to the gas separation performance. Herein, the polydopamine-derived submicrospheres (PDASS) were paired with polymers of intrinsic microporosity (PIM-1) to fabricate high-performance gas separation membranes, through which the effects of PDASS on gas permeability and CO2/N2 separation performance were systematically investigated. The addition of PDASS provides a 1.6-fold enhancement in CO2/N2 selectivity together with acceptable gas permeability as compared to the original polymeric membrane. Such enhanced separation behavior is supposed to stem from the densified membrane microstructure induced by the strong intermolecular interactions between PIM-1 and PDASS (i.e., charge transfer, π–π stacking, and hydrogen bonding). Importantly, the physical aging behavior, as judged by gas permeability, is retarded for PIM/PDASS membranes after 4 months of testing.

研究领域: 材料科学 · 化学工程 · 膜技术 · 气体分离
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Tartaric acid anion intercalated layered double hydroxides constructed a CO2-favorable transport channel in PIM-1 mixed matrix membranes for CO2/N2 separation

Caifeng Xia,Qikang Yin,Xinle Sun,Qinglong Liu,Sen Liu,Shuxian Wei,Siyuan Liu,Weifeng Lv,Zhaojie Wang,Xiaoqing Lu

As a unique polymer of intrinsic microporosity, PIM-1 has great potential in mixed matrix membranes (MMMs) for gas separation with ultra-high permeability. However, the separation performance, e.g. CO 2 /N 2 separation, is still limited by its poor selectivity. In this work, PIM-1-based MMMs containing tartaric acid anion intercalated layered double hydroxides (TA-LDH) nanofillers are successfully prepared. The uniformly dispersed TA-LDH in the PIM-1 matrix contributes to optimizing the stacking of polymer chains for accessible pores, which is conducive to CO 2 diffusion. In addition, the assistant experiment and theoretical calculation point out that the -COO - , –OH between the TA-LDH layers had an affinity for CO 2 , creating a two-dimensional fast transport channel between the enlarged interlayer space. Compared with the pristine PIM-1 membrane, the CO 2 permeability and CO 2 /N 2 selectivity of 0.7 % TA-LDH/PIM-1 membrane is increased by 43.19 % and 105.48 %. The excellent gas separation performance with CO 2 permeability of 8343.18 Barrer and CO 2 /N 2 selectivity of 39.02 exceeds the 2019 Robson upper limit. This paves a new way to improve the gas separation performance of PIM-1-based MMMs and suggests high perspectives for real applications.

CAS / MDL: 6381-59-5
研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Building well-defined magnetic channels in PIM-1 mixed matrix membranes with ZIF-8 wrapped Fe3O4 nanoparticle for effective O2/N2 separation

Yunxiang Bai,Xinxue Qiu,Deqiang Chen,Junwei Zheng,Liangliang Dong,Chunfang Zhang

Magnetic mixed matrix membranes (MMMs) show great potential for enhancing O 2 /N 2 separation efficiency by leveraging the inherent magnetic property differences between O 2 (paramagnetic) and N 2 (diamagnetic). However, one of the major challenges is the establishment and precise control of magnetic channels between magnetic fillers and polymer matrix. To address this issue, herein, ZIF-8 wrapped Fe 3 O 4 nanoparticles (Fe 3 O 4 @ZIF-8) were synthesized using a step-by-step assembly method, and then integrated into polymer of intrinsic microporosity (PIM-1) matrix to develop MMMs with well-defined magnetic channels for O 2 /N 2 separation. In comparison with Fe 3 O 4 , Fe 3 O 4 @ZIF-8 nanoparticles exhibited significantly enhanced compatibility with the polymer matrix, thereby facilitating uniform dispersion and improving interfacial adhesion. Gas permeation experiments revealed that the magnetic PIM-1/Fe 3 O 4 @ZIF-8 MMMs demonstrated enhanced O 2 /N 2 separation performance due to the combined effects of magnetic responsiveness and the presence of ZIF-8 magnetic channels. Under a magnetic field strength of 56mT, the magnetic MMM with a 4 wt% loading of Fe 3 O 4 @ZIF-8 exhibited optimal O 2 /N 2 separation performance with O 2 permeability of 710 Barrer and O 2 /N 2 selectivity of 3.64. These values represented a significant improvement of 42% and 24%, respectively, compared to pure PIM-1 membrane. Moreover, the simultaneous improvement of permeability and selectivity enabled the achievement of Robeson’s 2008 upper bound for O 2 /N 2 separation, underscoring the great potential of Fe 3 O 4 @ZIF-8 nanoparticles for designing magnetic MMMs with favorable structural attributes and exceptional separation efficiency.

研究领域: 材料科学 · 化学工程
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ADVANCED FUNCTIONAL MATERIALS · 2021 ·Vol. 31 ·期 47 ·2104830 · IF 18.808

PIM-1 as a Multifunctional Framework to Enable High-Performance Solid-State Lithium–Sulfur Batteries

Yuchen Ji,Kai Yang,Mingqiang Liu,Shiming Chen,Xinhua Liu,Biao Yang,Zijian Wang,Weiyuan Huang,Zhibo Song,Shida Xue,Yanda Fu,Luyi Yang,Thomas S. Miller,Feng Pan

Poly(ethylene oxide) (PEO) is a promising solid electrolyte material for solid-state lithium–sulfur (Li–S) batteries, but low intrinsic ionic conductivity, poor mechanical properties, and failure to hinder the polysulfide shuttle effect limits its application. Herein, a polymer of intrinsic microporosity (PIM) is synthesized and applied as an organic framework to comprehensively enhance the performance of PEO by forming a composite electrolyte (PEO-PIM). The unique structure of PIM-1 not only enhances the mechanical strength and hardness over the PEO electrolyte by an order of magnitude, increasing stability toward the metallic lithium anode but also increases its ionic conductivity by lowering the degree of crystallinity. Furthermore, the PIM-1 is shown to effectively trap lithium polysulfide species to mitigate against the detrimental polysulfide shuttle effect, as electrophilic 1,4-dicyanooxanthrene functional groups possess higher binding energy to polysulfides. Benefiting from these properties, the use of PEO-PIM composite electrolyte has achieved greatly improved rate performance, long-cycling stability, and excellent safety features for solid-state Li-S batteries. This methodology offers a new direction for the optimization of solid polymer electrolytes.

研究领域: 材料科学 · 电化学 · 电池技术
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JOURNAL OF POLYMER SCIENCE · 2022 ·Vol. 60 ·期 15 ·2298-2308 · IF 3.046

Improving aging resistance of PIM-1 thin films by nano-TiO2 filler used for robust solvent permeation

Zhaolai Huang,Jiaqi Li,Mengxiao Zhang,Weilin Feng,Chuanjie Fang,Liping Zhu

Polymers of intrinsic microporosity (PIMs) are promising materials for membrane separation because their special rigid and contorted structures contribute to high permeability. However, their chain rearrangement to fill excessive free volume makes the permeability stability a tough challenge. In this work, we report on a new use of rutile nano-TiO 2 to mitigate the physical aging of PIM-1 (a typical PIM) nanofilms for stable permeability by mixing matrix. It was shown that the PIM-1 membrane incorporated with nano-TiO 2 displayed remarkably higher aging resistance with a lower swelling degree in long-term ethanol soaking, having more stable ethanol permeance with only a 5% decrease after 35 days, lower than 25% of the pure one. The mechanism of anti-aging was revealed by molecular simulation, thermal, tensile mechanical, and dynamic mechanical analysis. It was found that nano-TiO 2 had good compatibility with PIM-1 due to strong coordination interaction, making its uniform dispersion in polymer. Additional solvent permeation channels were also created to increase solvent permeance without compromising solute rejection. Due to the reliable interaction of nano-TiO 2 , which makes particles serve as physical crosslinking points, the movement of PIM-1 chains was limited partially to mitigate aging, enabling PIM-1-based membranes to have robust solvent permeation. Graphical

研究领域: 材料科学 · 化学工程 · 高分子科学
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