SEPARATION AND PURIFICATION TECHNOLOGY
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2021
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IF 7.312
Haiqian Lian,Eryue Song,Bin Bao,Wenhe Yang,Yu Yang,Yichang Pan,Shengui Ju
Metal-organic frameworks (MOFs) as molecular sieve membrane materials have received extensive attention on the gas separation application. However, the membrane separation performance is extremely limited by its intrinsic stability of frameworks. The successful preparation of high-quality gas separation membranes with excellent stability remains a grand challenge. ZIF-302 is based on hydrophobic ligand in-situ design with a high-stabile chabazite (CHA) topology. Herein, we synthesized uniform ZIF-302 nanocrystals with exceptional stability by introducing a modulator. Correspondingly, the continuous dense ZIF-302 polycrystalline membranes were also prepared for the separation of H 2 , N 2 , CO 2 , CH 4 and other gases. The permeance of H 2 and separation factor for H 2 /CH 4 mixtures at 35 °C and 1 bar were 2.8 × 10 -8 mol m −2 s −1 Pa −1 and 51.5, respectively, exceeding the Robeson upper bound in 2008. Furthermore, the separation performance of the super-hydrophobic ZIF-302 membranes for humidified mixed gases can maintain more than 168 h at 35 °C, indicating reliable long-term operational stability. Therefore, the CHA-type ZIF-302 polycrystalline membrane is promising for actual industrial gas separation.
研究领域:
材料科学
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化学工程
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膜技术
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Rashida Shahbaz,Tianyou Li,Yongchao Sun,Samrina Sharif,Gaohong He,Canghai Ma
Mixed matrix membranes (MMMs) have emerged as promising materials for hydrogen separation, combining the processability of polymers with enhanced permeability and selectivity offered by inorganic fillers. However, challenges such as filler aggregation and poor polymer-filler interfacial compatibility limit their performance. In this study, amino-modified bimetallic ZIF (Zn/Co-ZIF-NH 2 ) was synthesized and employed as a novel nanofiller to fabricate 6FDA-DAM-based MMMs, aiming to improve interfacial compatibility between the filler and the polymer matrix. The incorporation of Co 2+ ions into ZIF-8-NH 2 introduced a synergistic effect, optimizing the balance between the rigidity and flexibility of metal-to-ligand bond linkage, while amino groups promoted robust interfacial interactions with the polymer matrix. Compared to the pure polymeric membrane, the MMMs incorporating 40 wt% MOF exhibited a significant enhancement in gas permeability, with H 2 permeability rising from 750 to 3273 Barrer and CO 2 permeability increasing from 840 to 2733 Barrer, corresponding to improvements of 336.4 % and 225 %, respectively. Simultaneously, H 2 /CH 4 and CO 2 /CH 4 selectivities increased to 33.7 and 28.1, representing improvements of 88.3 % and 41 % over the pristine polymer. These performance metrics exceed the 2008 Robeson upper bounds, demonstrating the effectiveness of Zn/Co-ZIF-NH 2 nanofillers in overcoming the permeability–selectivity trade-off. This study underscores the effectiveness of amino-modified bimetallic MOFs as advanced fillers for high-performance MMMs, particularly suited for hydrogen purification and CO 2 separation applications.
研究领域:
材料科学
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化学工程
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膜技术
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气体分离
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纳米技术
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2023
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IF 9.5
Zhuangzhuang Gao,Baoju Li,Zhan Li,Tongwen Yu,Shuchang Wang,Qianrong Fang,Shilun Qiu,Ming Xue
Metal–organic frameworks (MOFs) are promising candidates for the advanced membrane materials based on their diverse structures, modifiable pore environment, precise pore sizes, etc. Nevertheless, the use of supports and large amounts of solvents in traditional solvothermal synthesis of MOF membranes is considered inefficient, costly, and environmentally problematic, coupled with challenges in their scalable manufacturing. In this work, we report a solvent-free space-confined conversion (SFSC) approach for the fabrication of a series of free-standing MOF (ZIF-8, Zn(EtIm)2, and Zn2(BIm)4) membranes. This approach excludes the employment of solvents and supports that require tedious pretreatment and, thus, makes the process more environment-friendly and highly efficient. The free-standing membranes feature a robust and unique architecture, which comprise dense surface layers and highly porous interlayer with large amounts of irregular-shaped micron-scale pore cavities, inducing satisfactory H2/CO2 selectivities and exceptional H2 permeances. The ZIF-8 membrane affords a considerable H2 permeance of 2653.7 GPU with a competitive H2/CO2 selectivity of 17.1, and the Zn(EtIm)2 membrane exhibits a high H2/CO2 selectivity of 22.1 with an excellent H2 permeance (6268.7 GPU). The SFSC approach potentially provides a new pathway for preparing free-standing MOF membranes under solvent-free conditions, rendering it feasible for scale-up production of membrane materials for gas separation.
研究领域:
材料科学
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化学工程
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纳米材料
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气体分离
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环境友好合成
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膜技术
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多孔材料化学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Weijie Sun,Jiayou Liao,Lijing Yuan,Yuying Zhao,Jingqiong Lu,Jiwei Ma,Xianjie Meng,Yong Wang,Chengyun Gao,Jinping Li
An ideal gas separation membrane requires high permeability, selectivity, and mechanical flexibility. In this study, we developed functionalized polyimide precursors (coPI) by copolymerizing hydroxy-diamine, flexible diamine, and dianhydride, and then calcined to prepare the thermal rearranged (coTR) membranes. 1 H NMR and FTIR confirmed coPI synthesis, while tensile tests and DSC showed improved mechanical strength (51.84–72.74 N) and moderate glass transition temperatures (144–176 ℃) due to ether-oxygen segments and imide groups. SEM and SAXS revealed morphological changes in thermally rearranged (coTR) membranes. Gas permeation tests demonstrated that coTR-5, treated at 450 ℃, achieved an 18-fold increase in H 2 permeability (578.66 Barrer) with high H 2 /CH 4 selectivity (46.15), surpassing the 2008 Robeson limit. The membrane also exhibited flexibility, pressure tolerance, and long-term stability. Molecular dynamics simulations indicated a high free volume (18.75 %), highlighting ether-oxygen diamine copolymerization as an effective strategy for designing advanced TR membranes.
研究领域:
材料科学
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化学工程
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膜技术
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高分子化学
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气体分离
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Xiaoya Xu,Chengli Jiao,Xinxin Li,Xiaoqian Zhang,Lun Shu,Ge Su,Minghua Huang,Heqing Jiang
Metal-organic framework (MOF) membranes have emerged as promising candidates for hydrogen separation, but the fabrication of defect-free and flexible MOF membranes is still challenging. Here, we propose a thermally induced in-situ growth strategy to develop flexible membranes consisting of amorphous Zn-2-methylimidazole complex (a-Zn-MeIM) and crystalline zeolitic imidazolate framework-8 (c-ZIF-8) on polysulfone substrate, denoted as amorphous Zn-MeIM/crystalline ZIF-8 (a-Zn-MeIM/c-ZIF-8) membranes. During the thermal treatment of pre-sprayed mixture containing a-Zn-MeIM on the top surface of polysulfone substrate, a-Zn-MeIM is converted to c-ZIF-8. Similar coordination environments featured with Zn 2+ -2-methylimidazolate coordination configurations between flexible a-Zn-MeIM and rigid c-ZIF-8 provides enhanced interfacial compatibility, effectively eliminating cracks and grain boundary defects. Benefitting from both the flexibility of amorphous phase and well-defined pore structure of crystalline phase, the resulting a-Zn-MeIM/c-ZIF-8 membranes show flexibility and preferential diffusion of H 2 molecules. The membrane structure can be modulated by adjusting c-ZIF-8 concentration of sprayed colloid and thermal treatment temperature. The optimized a-Zn-MeIM/c-ZIF-8 3.75 membrane with flexibility exhibits a H 2 /CH 4 mixed separation selectivity up to 96.9 at 90°C. Additionally, a-Zn-MeIM/c-ZIF-8 3.75 membrane with an area of 644 cm 2 has been prepared, promoting the practical applications of MOF membranes with good processability.
研究领域:
材料科学
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化学工程
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膜技术
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
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IF 18.5
Keming Zhang,Xiaohe Tian,Zhe Xu,Haishan Huan,Rui Zhang,Xiaoting Feng,Qingnan Wang,Yanting Tang,Chenlu Liu,Shaofei Wang
Membrane-based gas separation offers notable energy efficiency benefits for hydrogen purification, yet it is often hindered by the inherent trade-off between permeability and selectivity. To address this challenge, a novel mixed matrix membrane (MMM) design is presented to boost H 2 separation performance via continuous hydrogen spillover mechanisms for the first time. The MMM incorporates a palladium-functionalized ZIF-67 gel (Pd@ZIF-67 gel) network into a polymer of intrinsic microporosity (PIM-1) matrix. The ZIF-67 gel network serves as a uniform dispersion medium for palladium nanoparticles (Pd NPs), thereby generating a multitude of active sites. These exposed sites, in conjunction with the microporous structure of ZIF-67, facilitate hydrogen dissociation and establish a continuous hydrogen spillover pathway throughout the membrane. This synergistic MMM design leads to substantial improvements in both hydrogen transport and selectivity. At an optimal loading of 28 wt% Pd@ZIF-67 gel, the MMMs exhibit a H 2 permeability of 3620 Barrer and a remarkable 417% enhancement in H 2 /CH 4 selectivity (24.9), surpassing the 2008 upper bound. This approach paves the way for the development of advanced materials tailored for gas separation applications.
研究领域:
材料科学
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化学工程
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膜技术
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气体分离
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
·
IF 19
Jiayi Liu,Yaohui Zhang,Yujie Ban,Weishen Yang
Emissions from the petrochemical industry often contain by-product hydrogen alongside various hydrocarbons, leading to both resource wastage and increased air pollution. The separation of H 2 from these hydrocarbons is thus of considerable economic and environmental importance. Conventional polymer membranes face inherent trade-offs between gas permeability and selectivity. To overcome this limitation, this study introduces a strategy to assemble metal–organic framework (MOF) nanoparticles into a sponge-like architecture on the surface of an ultrathin rubbery polysiloxane membrane, achieved by synergistically harnessing spin-coating-induced centrifugal forces and polymer–MOF chemical pinning forces. The resulting intricate sponge-like structure greatly promotes repeated adsorption–desorption cycles for the more condensable hydrocarbons, thereby markedly slowing their permeation through the membrane. The composite membrane achieves H 2 /CH 4 , H 2 /C 2 H 6 , and H 2 /C 3 H 8 separation factors of 136, 1370, and 1610, respectively, while maintaining H 2 permeances of 439 to 473 GPU. The membrane's effectiveness is further demonstrated for hydrogen separation from a simulated hydrocarbon-rich industrial tail gas: H 2 is enriched from 10% to 83% in the permeate. In doing so, the membrane not only efficiently recovers hydrogen but also reduce the combined emissions of six representative C 1 –C 4 hydrocarbons by 78%. This sponge-like MOF-polymer composite introduces a new paradigm for advanced H 2 /hydrocarbon separation membranes.
研究领域:
材料科学
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膜技术
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气体分离
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石油化工工程
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纳米材料
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环境工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）