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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Copolymerization with macrocyclic compound to prepare high-selectivity PIM-1-based carbon capture membranes

Zewen Xu,Pei Li,Hao Guo,Shengchao Zhao,Kuo Chen,Xinliang Liu,Ming Wang,Yingfei Hou

Excessive carbon emission leads to global warming, threatening human survival. Membrane-based carbon capture technology is an important component of carbon capture, utilization, and storage (CCUS) technology and one of the main upstream technologies for achieving carbon neutrality. PIM-1 materials exhibit high CO 2 permeability but lower CO 2 /N 2 selectivity, making it a significant focus to improve CO 2 /N 2 selectivity without sacrificing CO 2 permeability. In this work, Noria was introduced as a block through the bottom-up approach into the PIM-1 molecular chain, forming Noria-based porous organic polymer (NPOP) microregions with excellent CO 2 affinity. Additionally, the presence of NPOP increases the interchain gaps, resulting in a higher free volume. Consequently, the separation membrane prepared under optimal conditions broke the 2008 upper bound, with a 43.6 % increase in CO 2 permeability and a 41.7 % increase in CO 2 /N 2 selectivity. Furthermore, NPOP could form colloidal networks and provide rigidity to the separation membrane, endowing it with excellent aging resistance. After 6 months of aging, the CO 2 permeability of 0.5 %Noria decreased by only 33.4 % (67.4 % for pure PIM-1), indicating its strong potential for widespread applications.

CAS / MDL: 77-08-7
研究领域: 材料科学 · 环境科学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2023 · IF 6.1

Fabrication of Zr-MOF filled PVA/CS blended membranes for high efficiency CO2 separation

Beibei Zhang,Lihua Zhang,Jin Li,Jiawen Fu,Xiwei Qu

In the present work, a series of PVA and CS blend membranes were studied. These prepared membranes were evaluated by binary mixture gases of CO 2 /N 2 and CO 2 /CH 4 . The optimum ratio of PVA/CS for CO 2 permeance was achieved at 5:5. It recorded a CO 2 permeability of 20.8 GPU (1 GPU = 1 × 10 -6 ·cm 3 (STP)·cm −2 ·s −1 ·cmHg −1 ) with CO 2 /N 2 selectivity of 89.7, as well as CO 2 permeability of 10.2 GPU and CO 2 /CH 4 selectivity of 56.3. Secondly, two kinds of nanoparticle UiO-66 and UiO-66-NH 2 were used to prepare mixed matrix membranes. The effects of nanofiller content and chemical groups on gas permselectivity were investigated. Results show that the addition of nanoparticles can effectively improve the permselectivity of membrane. The mixed matrix membranes addition with UiO-66-NH 2 achieved the optimum CO 2 performance and these were following the order of PVA(5)/CS(5)-UiO-66-NH 2  > PVA(5)/CS(5)-UiO-66 > PVA(5)/CS(5). For all these membranes, the permeance and selectivity present initial increased and then decreased. Mixed matrix membranes addition UiO-66-NH 2 (containing 3.75 wt%) exhibits a CO 2 permeance of 32.77 GPU and CO 2 /N 2 selectivity of 93.47, as well as CO 2 permeance of 25.57 GPU and CO 2 /CH 4 selectivity of 70.1, which was beyond the 2008 Robeson upper bound.

研究领域: 材料科学 · 环境科学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2018 ·Vol. 135 ·期 46 ·46759 · IF 1.901

Bromomethylated poly(phenylene oxide) (BPPO)-assisted fabrication of UiO-66-NH2/BPPO/polyethersulfone mixed matrix membrane for enhanced gas separation

Mingmin Jia,Yi Feng,Jianhao Qiu,Xiaocheng Lin,Jianfeng Yao

UiO-66-NH 2 nanocrystals were synthesized and embedded into bromomethylated poly(phenylene oxide)/polyethersulfone (BPPO/PES) polymer matrix to form UiO-66-NH 2 /BPPO/PES mixed matrix membranes (MMMs). The crystalline structure, interaction between UiO-66-NH 2 and BPPO, and dispersion of UiO-66-NH 2 were characterized by FTIR, XRD, and SEM. Nanoparticle dispersion was drastically enhanced with the assistance of BPPO, giving an improved adhesion between the polymer and filler particles. Owing to the intrinsic adsorption property of UiO-66-NH 2 and BPPO to CO 2 , the CO 2 permeability was significantly increased. As a result, the UiO-66-NH 2 /BPPO/PES membrane exhibited enhanced gas separation performance, where CO 2 /N 2 and H 2 /N 2 ideal selectivities were increased to 50.2 and 302.4 with a CO 2 permeability of 125.6 Barrer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135 , 46759.

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 · 2024 · IF 8.4

Engineering the ultrathin polyamide nanofilm featuring high free volume via interfacial polymerization for efficient CO2 capture

Fei Shi,Qinghua Li,Ye Yuan,Yi Yang,Xingzhong Cao,Menglong Sheng,Song Zhao,Zhi Wang

Interfacial polymerization (IP) has been received as an indispensable technology to fabricate thin-film composite (TFC) membranes for gas separation because of the simple and designable process. However, achieving the highly permeable polyamide (PA) TFC membrane for CO 2 capture via the IP technique remains challenging. Herein, a highly CO 2 -permeable PA TFC membrane was synthesized by the polycondensation of N, N-Bis [3-(methylamino) propyl]methylamine (BMAPAm) and trimesoyl chloride (TMC). The ultrathin (∼47 nm) PA TFC membrane featuring with high free volume exhibited excellent CO 2 permeance with moderate CO 2 /N 2 selectivity. The causes of this desired structure were systematically investigated from the aspects of monomer supply and molecular structure, in which the 3,3′-diamino-N-methyldipropylamine (DNMDAm) was used as a comparison. The results illustrated the underlying monomer-structure-performance relationships of IP-made membranes, demonstrating the solid potential of the IP technology specifically toward high-performance CO 2 capture membranes. Finally, a pilot-scale continuous membrane fabrication process was demonstrated.

CAS / MDL: 2370-88-9
研究领域: 材料科学 · 环境工程
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JOURNAL OF MEMBRANE SCIENCE · 2014 · IF 4.908

Facilitated transport mixed matrix membranes incorporated with amine functionalized MCM-41 for enhanced gas separation properties

Hong Wu,Xueqin Li,Yifan Li,Shaofei Wang,Ruili Guo,Zhongyi Jiang,Chan Wu,Qingping Xin,Xia Lu

Facilitated transport mixed matrix membranes (FT-MMMs) were fabricated by incorporating polyethylenimine functionalized ordered mesoporous silica (PEI-MCM-41) into poly(ether-block-amide) (Pebax ® MH 1657). The polyethylenimine both in the pore channels and on the surface of MCM-41 rendered abundant amine carriers to facilitate the transport of CO 2 through reversible reaction and simultaneously improved the filler–polymer interface compatibility. The membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), tensile test, dynamic mechanical analysis (DMA), and X-ray diffraction (XRD). The results indicated that incorporation of PEI-MCM-41 generated stronger interfacial interactions and resulted in higher polymer chain rigidification at the filler–polymer interface compared with unmodified MCM-41. The as-prepared FT-MMMs showed increased gas permeability and selectivity, and the highest ideal selectivities for CO 2 /CH 4 and CO 2 /N 2 were 41 and 102 (at a CO 2 permeability of 1521   Barrer), respectively. Compared to the membranes doped with pristine MCM-41, the permeability, the ideal CO 2 /CH 4 selectivity and the ideal CO 2 /N 2 selectivity of the PEI-MCM-41-doped membranes were increased by 102.3%, 115.8% and 96.1%, respectively, at 20   wt% filler loading and surpassed the 2008 Robeson upper bound line.

CAS / MDL: 57-09-0
研究领域: 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

High performance membranes containing rigid contortion units prepared by interfacial polymerization for CO2 separation

Cuihua Ma,Qinghua Li,Zhi Wang,Min Gao,Jixiao Wang,Xingzhong Cao

Polymeric membranes have been widely researched for several decades due to their good processability and low cost. Herein, high-performance thin-film composite (TFC) membranes were prepared by interfacial polymerization using N-methyldiethanolamine (MEDA), 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethylspirobisindane (TTSBI) and trimesoylchloride (TMC). The effects of segmental chain motion on the gas separation performance of the TFC membranes were investigated for the polymeric membranes featuring rigid and contorted sites along the polymer backbone by inducting TTSBI. The results suggested that the introduction of rigid and contorted structures improved the cavities in the membrane, impeded the transport of larger gas, and enhanced the diffusive selectivity. Therefore, the TFC membrane exhibited high permeance and high selectivity with CO 2 permeance of about 1800 GPU and CO 2 /N 2 selectivity of 370 at 0.11 MPa, which is a remarkable improvement in gas separation performance.

CAS / MDL: 105-59-9 497-19-8
研究领域: 材料科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Highspeed transport pathway dominated by continuous arrangement of micron-sized hollow MOFs in MMMs to accelerate CO2 permeation

Wenji Zheng,Rui Ding,Ziheng Li,Xuehua Ruan,Yan Dai,Miao Yu,Xiangcun Li,Xiaoming Yan,Xiaobin Jiang,Xiujuan Zhang,Gaohong He

The hollow filler has been verified to effectively enhance the CO 2 permeability of mixed matrix membrane (MMMs) by constructing low-resistance transport pathway. However, the in-continuity of hollow fillers across the membrane results in insufficient CO 2 permeability. In this work, the micron-sized hollow ZIF-8 (Mic-H-ZIF-8) were designed and proposed to accumulate continuously across the membrane to construct the transport highway for CO 2 . Importantly, the in-situ polymerization was utilized to achieve continuous accumulation of the Mic-H-ZIF-8 fillers across the membrane. The Mic-H-ZIF-8 presents cavity size of 4 μm and shell thickness of 100 nm, and three or four Mic-H-ZIF-8 microspheres are aligned sequentially across the membrane, in which the effective gas transport distance is decreased from 13 μm to the range of 0.8–3 μm. Consequently, the CO 2 permeability of 5 wt% Mic-H-ZIF-8/PEO MMM is 224.6 % and 63.5 % higher than those of pure PEO membrane and nanosized hollow ZIF-8/PEO MMM at 0.1 MPa. Meanwhile, the CO 2 /N 2 selectivity is still as high as 70.0. This CO 2 separation performance is far exceeding the Robeson upper bound in 2008, and beyond the McKeown upper bound in 2019 as the feed pressure increasing, confirming the significance of continuous transport highway constructed by micron-sized hollow MOFs on improving CO 2 separation of MMMs.

研究领域: 材料科学 · 环境科学
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AICHE JOURNAL · 2025 · IF 4

Efficient CO2/CH4 separation achieved by metal–organic framework crystal-glass composite membranes

Xinrui Liu,De Ao,Mao Ye,Zhi Wang,Zhihua Qiao,Song Zhao

Metal–organic framework (MOF) glass holds great promise for gas separation applications. However, the inherent low porosity of MOF glass poses a considerable challenge in improving membrane permeability. In this work, a self-supporting MOF crystal-glass composite (CGC) membrane was synthesized via an innovative blending and melting approach, in which ZIF-62 powder was converted into an amorphous glassy phase and ZIF-9 powder was partially flux-melted, effectively preventing the reorganization of Zn─N bonds within ZIF-62. Consequently, the composite component structure significantly enhances the porosity and permeability of the MOF glass membrane. Furthermore, the incorporation of cobalt into the membrane matrix has notably enhanced its adsorption affinity for CO 2 , thereby boosting CO 2 /CH 4 selectivity. The resultant a g [(ZIF-9) 0.2 /(ZIF-62) 0.8 ] membrane has demonstrated exceptional CO 2 permeability of 20,324 barrer and superior CO 2 /CH 4 selectivity, both surpassing the 2018 upper bound. Thus, the innovative strategy for the design of MOF CGC membranes offers effective solutions to the challenges inherent in gas separation processes.

CAS / MDL: 5970-45-6
研究领域: 材料科学 · 环境科学 · 化学工程
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Diffusion-Regulated Interfacial Polymerization of Hierarchically Microporous Polyamide Membranes for Permselective Gas Separations

Ying Sun,Mingzhu Yan,Zhenyuan Li,Ling Wang,Xiaobo Chen,Shuangjiang Luo

Interfacial polymerization has emerged as a robust method for fabricating task-specific polyamide (PA) membranes. However, the limited microporosity of highly cross-linked PA membranes constrains their effectiveness in gas separation applications. Herein, we introduce an ionic liquid (IL)-regulated interfacial polymerization process to fabricate polyamide nanofilms incorporating kinked tetrakis (4-aminophenyl) methane monomers. In situ ultraviolet–visible spectroscopy demonstrates that the diffusion of 1,3,5-benzenetricarbonyl trichloride (TMC) toward the interface increases with the IL/H2O ratio, leading to the formation of a more compact membrane with a higher cross-linking degree. The PA-TAM7/3–60 min membrane exhibits a CO2 permeance of 29.8 GPU and a CO2/CH4 selectivity of 109, exceeding the 2008 Robeson upper bond. Additionally, the highly cross-linked structure imparts the membranes with notable plasticization resistance. Mixed-gas tests (CO2/CH4 = 50/50, v/v) reveal that the PA-TAM7/3–60 min membrane experiences only a 2% reduction in CO2 permeance and a 10% decrease in CO2/CH4 selectivity at a CO2 partial pressure of 300 PSIG, compared to its performance at 30 PSIG. The ease of tuning membrane structure and gas separation performance, along with its excellent plasticization resistance, underscores the potential of these PA membranes for task-specific gas separations.

CAS / MDL: 4422-95-1 540-84-1
研究领域: 材料科学 · 化学工程 · 环境科学
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Improving CO2 permeation and separation performance of CO2-philic polymer membrane by blending CO2 absorbents

Jun Cheng,Leiqing Hu,Yannan Li,Jianzhong Liu,Junhu Zhou,Kefa Cen

To research effects of CO 2 absorption capacity and type of CO 2 absorbent on the CO 2 separation and free-volume properties of facilitated transport membranes, two types of CO 2 absorbents, namely monoethanolamine (MEA) and ionic liquids (ILs:[P 66614 ][Triz] and [P 66614 ][2-Op]), were adopted. The CO 2 absorption capacities of MEA, [P 66614 ][Triz] and [P 66614 ][2-Op] were about 0.561   mol CO 2 per mol, 0.95   mol CO 2 per mol and 1.60   mol CO 2 per mol, respectively. All mean free-volume hole radiuses of membranes decreased after blending CO 2 absorbents. After polymer membrane blended with two ILs, number of free-volume hole increased, resulting in modest increase of the fractional free volume. Both CO 2 permeability and selectivity increased after blending MEA and ILs. The increasing range of CO 2 permeability corresponded with CO 2 absorption capacity of CO 2 absorbents, and membrane blending with [P 66614 ][2-Op] showed the highest CO 2 permeability of 672.1 Barrers at 25   °C. Pebax/PEGDME membrane blending with MEA obtained the highest CO 2 /H 2 and CO 2 /CH 4 selectivity at 17.8 and 20.5, respectively.

CAS / MDL: 142-58-5
研究领域: 材料科学 · 环境科学
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ADVANCED MATERIALS · 2020 ·Vol. 32 ·期 22 ·1907701 · IF 27.398

Unobstructed Ultrathin Gas Transport Channels in Composite Membranes by Interfacial Self-Assembly

Bo Wang,Zhihua Qiao,Jiayou Xu,Jixiao Wang,Xinlei Liu,Song Zhao,Zhi Wang,Michael D. Guiver

Ultrathin unobstructed gas transport channels through the membrane selective layer are constructed in mixed matrix membranes (MMMs) by using gravity-induced interface self-assembly of poly(vinylamine) and polymer-modified MIL-101(Cr). For CO 2 /N 2 (15/85 by volume) mixed gas, the MMMs achieve a high CO 2 permeance of 823 gas permeation units and CO 2 /N 2 selectivity of 242 at 0.5 MPa. Based on economic analyses, a two-stage membrane process can achieve gas separation and economic targets.

研究领域: 材料科学 · 化学工程
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RSC Advances · 2021 ·Vol. 12 ·期 1 ·517-527 · IF 3.361

Light-responsive metal–organic framework sheets constructed smart membranes with tunable transport channels for efficient gas separation

Qingping Xin,Meixue Zhao,Jianping Guo,Dandan Huang,Yinan Zeng,Yuhang Zhao,Teng Zhang,Lei Zhang,Shaofei Wang,Yuzhong Zhang

Exploring a new type of smart membrane with tunable separation performance is a promising area of research. In this study, new light-responsive metal–organic framework [Co(azpy)] sheets were prepared by a facile microwave method for the first time, and were then incorporated into a polymer matrix to fabricate smart mixed matrix membranes (MMMs) applied for flue gas desulfurization and decarburization. The smart MMMs exhibited significantly elevated SO2(CO2)/N2 selectivity by 184(166)% in comparison with an unfilled polymer membrane. The light-responsive characteristic of the smart MMMs was investigated, and the permeability and selectivity of the Co(azpy) sheets-loaded smart MMMs were able to respond to external light stimuli. In particular, the selectivity of the smart MMM at the Co(azpy) content of 20% for the SO2/N2 system could be switched between 341 and 211 in situ irradiated with Vis and UV light, while the SO2 permeability switched between 58 Barrer and 36 Barrer, respectively. This switching influence was mainly ascribed to the increased SO2 adsorption capacity in the visible light condition, as verified by adsorption test. The CO2 permeability and CO2/N2 selectivity of MMMs in the humidified state could achieve 248 Barrer and 103.2, surpassing the Robeson's upper bound reported in 2019.

CAS / MDL: 10026-24-1 97-67-6
研究领域: 材料科学 · 化学工程
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