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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2021 · IF 3.171

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Jing Dou,Shuo Han,Saisai Lin,Zhikan Yao,Lian Hou,Lin Zhang

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis (RO) membranes remains a considerable challenge. Herein, we proposed to introduce polymer of intrinsic microporosity, PIM-1, into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity. A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized. These designed characteristics endowed it with high solubility and reactivity. Then it was mixed with m -phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization. The characterization results exhibited that more “nodule” rather than “leaf” structure formed on RO membrane surface, which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains. In virtue of this effect, even with reduced surface roughness and unchanged layer thickness, the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L∙m −2 ∙h −1 with acceptable NaCl rejection of 97.6%. This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.

研究领域: 材料科学 · 环境工程
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MOLECULES · 2026 ·Vol. 31 ·期 4 ·753 · IF 5.1

Scaffold Hopping-Guided Design of Novel PIM-1 Inhibitors with Anticancer Activities

Yabing Xin,Qian Wu,Yitong Gao,Can Xiao,Qidong You,Zhengyu Jiang,Mengchen Lu

PIM kinases, as members of the serine/threonine kinase family, regulate key cellular processes such as proliferation, apoptosis, and metabolism by phosphorylating multiple substrates, making them important therapeutic targets for cancer treatment. In this study, we reported a series of structurally novel PIM-1 kinase inhibitors based on a scaffold-hopping strategy. After multiple rounds of structural optimization, the highly active compoundC2was obtained, exhibiting an IC50of 33.02 ± 1.31 nM against PIM-1 kinase. Molecular docking results revealed that compoundC2stably bound to the hydrophobic cavity of the PIM-1 protein and formed hydrogen bond interactions with polar residues in the hinge region, thereby effectively inhibiting kinase activity. In vitro antitumor assessment demonstrated significant proliferation inhibition of the hematological tumor cell line MM.1S (IC50= 1.87 μM), comparable to the positive controlSGI-1776(IC50= 1.71 μM). In addition, compoundC2possessed favorable drug-like properties and excellent stability in simulated gastrointestinal fluids and rat plasma. This study provides promising lead compounds for the development of novel PIM-1-targeted anticancer drugs, which can be further optimized.

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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Exploration of modified Polymers of Intrinsic Microporosity (PIM) for extracorporeal membrane oxygenator (ECMO)

Xingci Liu,Yu Bai,Yiling Liu,Chong Cheng,Shudong Sun,Changsheng Zhao

Extracorporeal Membrane Oxygenation (ECMO) is the most important supporting therapy to rescue patients with respiratory distress syndrome (ARDS), for which the membrane oxygenator offers a place for CO 2 and O 2 exchange. Although Poly (4-methyl-1-pentene) (PMP) has been extensively used as ECMO material, the problems of protein adsorption fouling and the need for anticoagulation remain challenging for clinical applications. Additionally, the challenges associated with the functional modification of PMP material underscore the importance of finding a new material with excellent gas permeability and blood compatibility. On the other hand, Polymers of Intrinsic Microporosity (PIM) has been extensively studied in the field of gas separation due to their unique twisted helical structure and high free volume. However, its hydrophobic nature also raises concerns about its anti-fouling ability and hemocompatibility, which restricts the exploration of PIM in ECMO applications. Herein, we modify the PIM-1 membrane and study the hemocompatibility of PIM-1, carboxylated-PIM-1, and amidoxime-functionalized-PIM-1, and explore their gas permeability by molecular dynamics simulation and experimental verification. The modified PIM membranes exhibit remarkable comprehensive performance, including effective anti-protein adhesion and hemocompatibility, high oxygen permeability, and CO 2 removal rate. Blood oxygenation tests also reveal that the modified membranes prepared in this work fully meet practical requirements, exhibiting great application potential.

研究领域: 生物医学工程 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Robust fluorescent detection of iodine vapor by a film sensor based on a polymer of intrinsic microporosity

Xinbo Wang,Cong Yu,Hao Guo,Yongqiang Cheng,Yanwei Li,Daoyuan Zheng,Shanshan Feng,Yanxin Lin

Rapid and high-fidelity detection of radiological iodine species are of extreme importance for the safety of the population and the environment in nuclear fuel reprocessing or in case of nuclear accidents. A simple and universal method to fabricate the sensor to user-friendly devices toward a desired analytical environment would further benefit its applications. Herein, we describe the success of using luminescent spectroscopy for off- and on-line detection of gaseous iodine by a fluorescent film sensor based on a polymer of intrinsic microporosity (PIM-1), a material that possesses intrinsic signal amplification capability and good solubility for processing into desired morphologies. Due to the photoinduced electron transfer (PET) effect, the fluorescence of PIM-1 is quenched drastically upon I 2 exposure, but not much altered by H 2 O, CO 2 , or H 2 S. An off-line I 2 sensor of free-standing PIM-1 membrane and a real-time flue I 2 detector by coating PIM-1 film inside a capillary tube were fabricated and applied. Quick response (few seconds), high signal–noise ratio (five orders of magnitude), low detection limit (few ppb), steam tolerability, as well high reversibility and reusability were achieved, making the material a practically convenient and efficient I 2 sensor.

CAS / MDL: 1835-49-0
研究领域: 材料科学 · 环境科学
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JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

Synergistic tuning mixed matrix membranes by Ag+-doping in UiO-66-NH2/polymers of intrinsic microporosity for remarkable CO2/N2 separation

Zhihong Lin,Ziyi Yuan,Kaifang Wang,Xuezhong He

Novel mixed matrix membranes (MMMs) with superior CO 2 /N 2 separation properties are of great importance for post-combustion CO 2 capture from flue gas . Metal-organic frameworks (MOFs) as one of the most attractive porous fillers for MMMs fabrication, are considered to provide a solid molecular sieving mechanism for enhancing CO 2 /N 2 selectivity. However, it causes the reduction in gas permeability and limits its further industrialization. Herein, we proposed a new strategy for filler functionalization by doping silver ions (Ag + ) into UiO-66-NH 2 nanoparticles through the double-solvent method and used for the preparation of advanced MMMs. The double-solvent method is benefits for the enrichment of Ag + in the hydrophilic pores of UiO-66-NH 2 . As a result, the prepared novel MMMs called Ag + @UiO@PIM-1 with the polymers of intrinsic microporosity (PIMs) as polymer matrix , show outstanding CO 2 permeability. According to the mixed gases (CO 2 /N 2  = 10:90) permeation experiments under 25 °C and 2 bar, the membrane with 30%Ag + @10%UiO loading achieves more than 65% increase in CO 2 /N 2 selectivity (∼30) and 120% in CO 2 permeability (>15,000 Barrer) compared to the pristine PIM-1 membrane. By optimizing the Ag + doping amount and Ag + @UiO loading content, the separation performance exceeds the 2019 CO 2 /N 2 upper bound. To figure out the separation mechanism, the pore texture properties and CO 2 affinity of the functional filler (Ag + @UiO) together with the membrane structure were characterized by XPS , PXRD , SEM, gas sorption , etc. The synergistic mechanisms by combing CO 2 facilitated transport and molecular sieving from pore regulation were identified to enable advanced CO 2 /N 2 membrane separation .

研究领域: 材料科学 · 环境工程
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Membranes · 2021 ·Vol. 11 ·期 1 ·35 · IF 4.106

Preparation of Amino-Functional UiO-66/PIMs Mixed Matrix Membranes with [bmim][Tf2N] as Regulator for Enhanced Gas Separation

Jiangfeng Lu,Xu Zhang,Lusheng Xu,Guoliang Zhang,Jiuhan Zheng,Zhaowei Tong,Chong Shen,Qin Meng

Development of mixed matrix membranes (MMMs) with excellent permeance and selectivity applied for gas separation has been the focus of world attention. However, preparation of high-quality MMMs still remains a big challenge due to the lack of enough interfacial interaction. Herein, ionic liquid (IL)-modified UiO-66-NH2filler was first incorporated into microporous organic polymer material (PIM-1) to prepare dense and defect-free mixed matrix membranes via a coating modification and priming technique. IL [bmim][Tf2N] not only improves the hydrophobicity of UiO-66-NH2and facilitates better dispersion of UiO-66-NH2nanoparticles into PIM-1 matrix, but also promotes the affinity between MOFs and polymer, sharply reducing interface non-selective defects of MMMs. By using this strategy, we can not only facilely synthesize high-quality MMMs ignoring non-selective interfacial voids, but also structurally regulate MOF nanoparticles in the polymer substrate and greatly improve interface compatibility and stability of MMMs. The method also gives suitable level of generality for fabrication of versatile defect-free MMMs based on different combination of MOFs and PIMs. The prepared UiO-66-NH2@IL/PIM-1 membrane exhibited outstanding gas separation behavior with large CO2permeation of 8283.4 Barrer and high CO2/N2selectivity of 22.5.Keywords:mixed matrix membrane;amino-functional UiO-66;PIM-1;[bmim][Tf2N];gas separation

CAS / MDL: 10026-11-6
研究领域: 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2019 · IF 7.015

Mixed matrix membranes derived from nanoscale porous organic frameworks for permeable and selective CO2 separation

Guangli Yu,Yanqin Li,Ziyang Wang,Terence Xiaoteng Liu,Guangshan Zhu,Xiaoqin Zou

Membrane separation has great potential for carbon dioxide capture. We have been developing porous organic frameworks (POFs) as a new class of nanofillers for mixed matrix membranes fabrication. A triangle monomer of melamine (MA) reacts with another linear monomer of 1, 4-piperazinedicarboxaldehyde (PDA) in a microwave system to form the POF material (designated as MAPDA). As-synthesized MAPDA possesses an open framework featured with high surface area of 548.3 m 2  g −1 and a large pore of ~1.0 nm. SEM shows that MAPDA particles are in size of ~42 nm, and adsorption measurement reveals that MAPDA is favorable for adsorbing CO 2 with an uptake of 47.0 cm 3  g −1 at 298 K and 101 kPa. Mixed matrix membranes of MAPDA/PIM-1 with different MAPDA loadings (0–20 wt%) are produced by blending nanofillers of MAPDA and soluble matrices of PIM-1. Single gas permeations demonstrate that CO 2 permeability is increased dramatically from 3694.5 to 7861.9 Barrer, meanwhile the CO 2 /N 2 selectivity is enhanced from 18.9 to 23.9 for pure PIM-1 and for a representative membrane of MAPDA/PIM-1 with 15 wt% MAPDA. High porosity and molecular affinity make the predominant contribution to the enhancements of CO 2 permeability and CO 2 /N 2 selectivity. MAPDA/PIM-1 membranes are also very selective for capturing CO 2 from gas mixtures of 50CO 2 :50N 2 and 15CO 2 :85N 2 with separation performances exceeding the latest upper bound. The good separation property and the high stability of MAPDA/PIM-1 have shed a light on next-generation membrane for CO 2 separation development.

CAS / MDL: 67-68-5 108-78-1
研究领域: 材料科学 · 环境工程
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JOURNAL OF MEMBRANE SCIENCE · 2017 · IF 6.035

Enhanced CO2 selectivities by incorporating CO2-philic PEG-POSS into polymers of intrinsic microporosity membrane

Leixin Yang,Zhizhang Tian,Xiyuan Zhang,Xingyu Wu,Yingzhen Wu,Yanan Wang,Dongdong Peng,Shaofei Wang,Hong Wu,Zhongyi Jiang

The urgent demand of capturing CO 2 from energy relevant applications stimulated researchers to develop novel high-performance membrane materials. PIM-1, a representative class of polymers of intrinsic microporosity (PIMs), possesses high permeability but low selectivity due to its highly twisted ladder-like structure. A facile approach to improve CO 2 separation performance of PIM-1 is to implant CO 2 -philic fillers. In this study, a novel nano-sized filler Poly(ethylene glycol) functionalized Polyhedral oligomeric (PEG-POSS), with PEG anchored on POSS was incorporated into PIM-1 membrane at nanoscale level to increment CO 2 selectivities of the membrane. The as-prepared PIM-1/PEG-POSS mixed matrix membranes (MMMs) were characterized by Fourier transform infrared (FT-IR) spectra, thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Single gas permeabilities of N 2 , CH 4 and CO 2 were measured by the time-lag method. PIM-1/PEG-POSS membranes showed enhanced CO 2 selectivity over CH 4 and N 2 at high PEG-POSS loadings. Specifically, the PIM-1/PEG-POSS membrane with 10   wt% PEG-POSS nanoparticles exhibited the optimal separation performance, of which the CO 2 permeability reached 1300 Barrer and CO 2 /CH 4 selectivity increased by 150% compared with the pristine PIM-1, which surpassed the 2008 Robeson upper bound. The as-prepared PIM-1/PEG-POSS MMMs show great potential for CO 2 capture.

CAS / MDL: 1835-49-0 584-08-7
研究领域: 材料科学 · 环境科学
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

CO2 separation performance for PIM based mixed matrix membranes embedded by superbase ionic liquids

Jiuli Han,Haiyan Jiang,Shaojuan Zeng,Yinge Bai,Xiangping Zhang,Lu Bai

Mixed matrix membranes (MMMs) have drawn much interest in CO 2 separation due to their excellent separation performance, mechanical property, and desirable processability. However, obtaining highly compatible MMMs is a great challenge and is vital to avoid the loss of the separation selectivity of the MMMs. In this work, superbase ionic liquid (1,8-diazabicyclo[5,4,0]undec-7-ene imidazole ([HDBU][Im])) was used as a wetting agent to increase the interfacial compatibility between ZIF-67 and PIM-1, hence improving the membrane gas separation. [HDBU][Im] embeding into the MMMs could efficiently enhance the compatibility and diminish the interfacial voids. Furthermore, incorporating 5 wt% [HDBU][Im]@ZIF-67 nanocomposite into the PIM-1 matrix improves the gas permeability and CO 2 selectivity. The separation performances under the different temperatures were also conducted and showed that reducing temperature slightly decreases the gas permeability but significantly increases the CO 2 /CH 4 selectivity via enhancing the CO 2 solubility. The permeation active energies, diffusivities and solubilities were obtained to explain the gas permeate mechanism.

研究领域: 材料科学 · 化学工程
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CHEMICAL ENGINEERING SCIENCE · 2020 · IF 3.871

Incorporating nano-sized ZIF-67 to enhance selectivity of polymers of intrinsic microporosity membranes for biogas upgrading

Chumei Ye,Xingyu Wu,Hong Wu,Leixin Yang,Yanxiong Ren,Yingzhen Wu,Yutao Liu,Zheyuan Guo,Rui Zhao,Zhongyi Jiang

Membrane-based separations are of energy-efficient and environmentally benign attributes for biogas energy developments. Membranes from polymers of intrinsic microporosity (PIMs) often suffer from low selectivity. In this study, remarkable enhancements in CO 2 /CH 4 selectivity of PIM-1 membranes are achieved by incorporating nano-sized ZIF-67 (ZIF-S) filler with a larger specific surface area and a better compatibility, thereby fortifying the interactions with PIM-1 matrix and effectively alleviating nonselective interfacial voids. For the resulting PIM-1/ZIF-S membranes, a maximum CO 2 /CH 4 selectivity of 21.1 was acquired with 15 wt% loading of ZIF-S, an increase of 69.40% compared with the pristine PIM-1 membrane, along with an associated CO 2 permeability above 2800 Barrer. To elucidate gas transport behaviors within membranes, a modified Maxwell model is developed and the calculation results match well with the experimental data. The strategy of incorporating framework nanofillers into membranes may find promising applications in enhancing the selectivity of highly permeable polymer membranes.

研究领域: 材料科学 · 环境工程 · 能源技术
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ACS Applied Materials & Interfaces · 2025 · IF 8.2

Ionic Liquid-Functionalized Defective MOFs for Membrane-Based CO2 Separation: A Dual Optimization Approach for Interface and Transport

Zongkai Liu,Haofan Zhao,Bingquan Hua,Yan Wang,Tianyou Lu,Meng Guo,Guanying Dong,Junyong Zhu,Yatao Zhang

Defective MOFs have been identified as promising candidates for efficient membrane-based separation applications. However, the utilization of defective MOFs in membrane gas separation is still in its infancy due primarily to the inefficient molecular differentiation induced by structural defects. Herein, we report a strategic combination of ionic liquid (IL) and defective UiO-66-NH2 MOF to ameliorate the CO2/N2 selectivity within the highly permeable PIM-1 polymer. Characterizations and analysis have shown that postmodification of defective UiO-66-NH2 with IL greatly improved its dispersion and compatibility within PIM-1. Meanwhile, the CO2-philic nature of IL facilitated increased adsorption of CO2 molecules, enabling them to pass rapidly through the transport channels in defective MOF. As a result, the optimal membranes demonstrated a concurrent enhancement in both the CO2 permeability and the CO2/N2 ideal selectivity, which were 197.1% and 24.9% greater than those of PIM-1, respectively. Additionally, the complex Lewis acid/base and hydrogen bonding interactions among IL/defective MOF/PIM-1 have ensured that the resulting membranes possess long-term operational durability and significant antiaging behavior. This deliberate matching between IL and defective MOFs has well circumvented the potential limitation of defective MOFs for carbon capture, with potential applications in other areas.

CAS / MDL: 10312-55-7 10026-11-6
研究领域: 材料科学 · 环境工程
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ACS Applied Polymer Materials · 2026 · IF 5.2

Synthesis of CO2-Selective PIM-1 Composite Membranes via Spin-Coating and Thermal Treatment of Polyimidazolium

Eun Kyu Sun,Kyungwhan Min,Ook Choi,Senthil Kannan,Tae-Hyun Kim

Polymer of intrinsic microporosity-1 (PIM-1) is recognized for its exceptional gas permeability, attributed to its high free volume and microporosity. However, it presents several disadvantages, including low selectivity, plasticization, and poor aging properties. To address these challenges, PIM-nPI-Tz, a series of composite membranes containing triazine cross-links, was developed herein by spin-coating nitrile-functionalized polyimidazolium (PI-CN) onto a PIM-1 membrane, followed by heat treatment. The resulting coating layer increased the selectivity of the PIM-1 membrane, given its CO2 affinity, while the formation of triazine increased the backbone-to-backbone spacing, enhancing the diffusivity and permeability of the membrane. Notably, PIM-5PI-Tz (involving PIM-1 coated with a 5% PI-CN solution) exhibited a 73% increase in CO2 permeability (7539 barrer) and a 34% rise in CO2/N2 selectivity (24.4), nearly equivalent to the 2019 Robeson upper bound in terms of overall gas separation. Moreover, the plasticization of the membrane was effectively suppressed, even at a feed gas pressure of 20 bar. Further, its gas separation performance was retained over 300 days under CO2/N2 mixed-gas conditions, demonstrating its superior antiplasticization and antiaging characteristics. The coating material used herein, PI-CN, exhibits a significantly higher CO2-philicity than conventional coating materials, such as Pebax, PEG, and PDMS. Moreover, during the spin-coating and subsequent heat treatment processes, molecular rearrangement within PI-CN facilitates CO2 diffusion, further enhancing the gas transport performance of the PIM membrane.

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