EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2018
·Vol. 2018
·期 8
·1047-1052
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IF 2.507
Xiaoxia Jia,Ning Yuan,Li Wang,Jiangfeng Yang,Jinping Li
Graphical Both high selectivity and adsorption capacity in the adsorptive separation of CO 2 , CH 4 , and N 2 were achieved by means of (CH 3 ) 2 NH functionalization of the unsaturated metal sites of the MOF Ni-HKUST-1. Ni-HKUST-1, with the same topological structure as Cu-BTC (HKUST-1), was synthesized by a (CH 3 ) 2 NH-assisted method. Ni-HKUST-1 with high purity (> 90 %), yield (85 %), and BET surface area (1088 m 2 /g) was successfully synthesized for the first time by using NiCl 2 . The pure-component adsorption isotherms of CO 2 , CH 4 , and N 2 on Ni-HKUST-1 were measured by the volumetric method and the data used to estimate the separation selectivity for CO 2 /CH 4 , CH 4 /N 2 , and CO 2 /N 2 binary mixtures according to the ideal adsorbed solutions theory. At 273 K and 1 atm, the selectivities for CO 2 /CH 4 , CH 4 /N 2 , and CO 2 /N 2 were 14.49, 5.36, and 183.41, respectively, and the adsorption capacities for CO 2 and CH 4 were 223.87 and 67.89 cm 3 /g, respectively. This is a rare demonstration of both high selectivity and adsorption capacity in the separation of CO 2 , CH 4 , and N 2 .
研究领域:
材料科学
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化学工程
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环境科学
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高影响因子
ENERGY
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2022
·
IF 8.857
Haorui Liu,Shuoyu Wang,Xiaoqiong Wang,XiaoJing Feng,Shuixia Chen
A novel stable porous solid amine adsorbent with three-dimensional interpenetrating network structure was prepared by polymerization of divinylbenzene using high internal phase emulsion (HIPE) template method , and followed by further introducing polyethyleneimine (PEI) by impregnation-crosslinking method. Fixed bed dynamic adsorption experiment proved that under wet condition, the former exhibited not only a higher capacity of 6.22 mmol/g but also a better adsorption kinetics process with faster adsorption rate and longer lag in breakthrough point, which makes it potential to be used in gas separation. In CO 2 /CH 4 separation experiment, PolyHIPE-PE30-4 showed a CO 2 /CH 4 separation selectivity of 253 at 298 K and 1 bar, and meanwhile exhibited an extra-high operating capacity. The pure methane productivity of PolyHIPE-PE30-4 was 24.1 mmol/g from CO 2 /CH 4 (80:20, v/v) mixed gas, 4.5 times to that of PE30-4 gel (5.36 mmol/g). Significantly, PolyHIPE-PE30-4 could maintain an excellent regeneration performance after at least 7 cycles, while PolyHIPE-P30 exhibited a remarkably decrease in adsorption capacity after only three adsorption-desorption process in wet condition, demonstrating the advantage of impregnation-crosslinking method for amine functionalization. The superior CO 2 adsorption capacity and regeneration stability, combined with its superior adsorption kinetics property make it a broad prospect in the field of CO 2 /CH 4 separation.
研究领域:
化学工程
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环境科学
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高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2025
·
IF 4.7
Lili Gong,Ju Bai,Can Wang,Zhenyuan Li,Linglong Shan
Two-dimensional (2D) metal-organic framework (MOF) nanosheets are promising fillers for gas separation membranes, owing to their high aspect ratios and tunable pore architectures. Realizing their full application potential requires precise control over nanosheet morphology and sizes to optimize membrane performance. This work employs crystal growth kinetics modulation to tailor the morphology and size of ZIF-67-based nanosheets incorporated into mixed matrix membranes (MMMs) targeting superior CO 2 /CH 4 separation. Strategy (i): Adjusting early-stage nucleation kinetics yielded two distinct ZIF-L nanosheet types: disk-like (ZIF-L-I) and leaf-like (ZIF-L-II). ZIF-L-II, synthesized with higher ligand molar ratio, possessed larger lateral dimensions and more favorable pore characteristics, significantly enhancing gas separation. Strategy (ii): Amino-functionalized ionic liquid (IL) was introduced to further modulate the size of ZIF-L-II nanosheets. The IL's amino groups served as capping agents by coordinating preferentially with Co ions, restricting framework extension without altering crystallinity. The ILs loading amount dictated the final nanosheet size, but did not alter their crystalline phase. Critically, the IL also exhibits affinity for CO 2 , augmenting its transport. At 48 % IL addition, the CO 2 permeability of the 10 wt% IL-ZIF-L-II/PI membrane surged from 289 Barrer to 493 Barrer, without significant selectivity loss. The synergistic combination of kinetically-controlled synthesis (yielding larger and leaf-like nanosheets) and IL-mediated size regulation (providing both capping and CO 2 -philic functions) resulted in a 70 % enhancement in CO 2 permeability.
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ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Xupeng Zhang,Kaiqian Li,Longxin Guo,Zhiping Xu,Shuduan Deng,Ying Liu,Gang Zhu
To effectively mitigate the global warming problem caused by excessive CO2 emissions, the implementation of direct air capture (DAC) technology has emerged as one of the most promising strategies for capturing CO2 from the atmosphere. The key to DAC technology hinges on the development of high-performance solid sorbent materials that demonstrate high CO2 adsorption capacity and gas separation selectivity, particularly under low CO2 partial pressure conditions. Herein, we have successfully developed a class of MOF@carboxylated wood sponge (MOF@CWS) hybrid sorbents, capable of efficient CO2 capture from low-concentration (less than 10,000 ppm) CO2 sources, achieved by embedding the porous MOF into carboxylated wood sponges (CWS) substrate via an in situ growth route. Within the MOF@CWS series, the CO2 uptake capacity of Mg-MOF-74@CWS is 3.61 and 2.65 mmol/g at 1 bar, 273 and 298 K, respectively, significantly higher than those of CWS and HKUST-1@CWS. Moreover, this material exhibited outstanding DAC performance, with the CO2 sorption capacity at 273 K up to 0.56 mmol/g from ambient air (ca. 400 ppm of CO2), surpassing most other solid sorbents. The obtained Mg-MOF-74@CWS also demonstrated exceptional CO2/CH4 separation performance, primarily due to the unique pore structure and augmented interaction between the CO2 molecules and the hybrid sorbents. The results of this study indicate that Mg-MOF-74@CWS has potential as an efficient solid sorbent for the DAC of CO2.
研究领域:
材料科学
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环境科学
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化学工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Daofei Lv,JiaYu Chen,Kexin Yang,Houxiao Wu,Yongwei Chen,Chongxiong Duan,Ying Wu,Jing Xiao,Hongxia Xi,Zhong Li,Qibin Xia
Using porous materials to selectively adsorb CO 2 from flue gas or natural gas is a promising method for mitigating CO 2 emission and purifying methane. Here, we synthesized an L-aspartic acid based microporous metal-organic framework (MIP-202) and studied its adsorptive separation performance for CO 2 /CH 4 and CO 2 /N 2 mixtures. Results show that MIP-202 had ultrahigh CO 2 /CH 4 (72.9 and 241.5 for CO 2 /CH 4 = 50/50 and 10/90, respectively) and CO 2 /N 2 (1,950,000 and 2129.1 for CO 2 /N 2 = 50/50 and 15/85, respectively) IAST selectivities at 298 K and 100 kPa. The high selectivity was verified by the calculations of Henery’s law selectivity and breakthrough experiments. Metropolis Monte Carlo simulation calculations show that CO 2 with greater polarizability and quadruple moment tends to occupy the pore walls of large cages with higher polarity, while the less polar CH 4 or N 2 majorly being adsorbed in the pore walls of small cages with lower polarity, resulting in the ultrahigh CO 2 /CH 4 and CO 2 /N 2 separation selectivities. MIP-202 exhibits low CO 2 adsorption enthalpy (17.2–30.7 kJ/mol), superior persistent reusability after five cyclic adsorption experiments, easy desorption performance at 298 K, moderate water and moisture stability, good stability under dry and humid SO 2 atmosphere, and low ligand cost ($36/kg). MIP-202 extrudates were prepared by an extrusion molding method using hydroxypropyl cellulose (HPC) as the binder and they retained 97.35% CO 2 uptake of MIP-202 powder at room temperature and pressure. This work shows that MIP-202 is an industrially promising material for the separation of CO 2 /CH 4 and CO 2 /N 2 mixtures.
研究领域:
材料科学
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环境科学
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高影响因子
POLYMER
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2022
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IF 4.432
Min Zhao,Caili Zhang,Yunxuan Weng,Pei Li
Thermal oxidative crosslinking results in the generation of oxygen bridges among polymer chains and helps regulate the membrane microstructure. Simultaneously, any strategy to increase the crosslinking sites of polyimide (PI) can improve the crosslinking efficiency and allow precise control of the pore structure of membranes. Phenolphthalein-based PIs are potentially suitable precursors for thermal oxidative crosslinking of membranes, since thermal treatment will result in the degradation of lactone ring leading to the generation of a pair of phenyl crosslinking sites. In this work, three phenolphthalein-based diamines with different structures were designed and synthesized. The three diamines were subsequently reacted with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) to prepare phenolphthalein-based PIs. The original membranes were post-treated by thermal oxidation crosslinking at 400 °C and 425 °C, respectively; the lactone ring underwent decomposition, and the imide ring opened at the same time, resulting in the generation of multiple crosslinking sites and correspondingly improving the crosslinking efficiency. The effect of the side groups (−CH 3 , –CF 3 or unsubstituted) of phenolphthalein-based diamine and thermal treatment temperatures on the gas separation performance of phenolphthalein-based PI membranes were investigated. Wide-angle X-ray diffractometry (WAXD) and wide-angle X-ray scattering (WAXS) analysis demonstrated that the π-π stacking distance were improved. BTDA-FPP-425 had a CO 2 /CH 4 selectivity of 37.68. This thermal degradation along with thermal oxidative crosslinking strategy provides a promising approach for fabrication of CO 2 /CH 4 separation membrane .
研究领域:
材料科学
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化学工程
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Ke Chen,Linhan Ni,Xin Guo,Chengming Xiao,Yue Yang,Yujun Zhou,Zhigao Zhu,Junwen Qi,Jiansheng Li
The performance of mixed matrix membranes (MMMs) substantively depends on the intrinsic structure and composition of the introduced nanofillers. In this work, pyrazole-based metal-organic frameworks (termed as MOF-303) were introduced into polymer of intrinsic microporosity (PIM-1) through a physical blending approach. Thanks to the well CO 2 -philic capability, high porosity, and appropriate pore structure of the incorporated MOF-303, the obtained MMMs exhibited remarkable separation performance. The improved CO 2 permeability and well-maintained CO 2 /CH 4 selectivity were achieved. Specifically, MMMs introducing 30 wt% MOF-303 loading exhibited a CO 2 /CH 4 selectivity of 27.6 and a high-CO 2 permeability of 7528.2 Barrer, which were 2.2 and 1.9 times greater than those of the unfilled PIM-1 membranes, respectively. Furthermore, a 33-h continuous separation test verified the excellent stability of the manufactured MMMs. More importantly, the MMMs showed significant resistance against physical aging, retaining up to 92.8% of their original CO 2 permeability after 150 days, compared to just 33.0% for control PIM-1 over the same period. Meanwhile, the plasticization resistance of the MMMs was reinforced compared to the unfilled PIM-1 membrane. This study potentially provides a novel approach for the rational design of MMMs in CO 2 separation applications.
研究领域:
材料科学
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环境科学
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高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2026
·Vol. 71
·期 8
·3669-3680
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IF 2.4
Wu Shasha,Li Wenyu,Yang Li,Chen Zhen,Qin Yuanhang,Yuan Lunyong,Sun Wei
This study systematically investigates the influence
of lithium
nitrate (LiNO 3 ) modification on the gas adsorption characteristics
of UiO-66. The adsorption isotherms for carbon dioxide (CO 2 ), methane (CH 4 ), and nitrogen (N 2 ) were acquired
within a pressure range of 0 to 20 bar. The results from the cyclic
testing indicate that the UiO-66–0.05LiNO 3 variant
exhibits commendable stability. Notably, the incorporation of LiNO 3 enhances the CO 2 adsorption capacity by 29.48%,
reaching 2.24 mmol·g –1 at a pressure of 1 bar.
This is attributed to the introduction of lithium ions, which enhance
the electrostatic interaction between CO 2 and the MOF.
Analysis of the high-pressure data reveals that the Langmuir–Freundlich
model provides the most robust fit, whereas the Langmuir and Dual-site
Langmuir models demonstrate increased discrepancies as pressure escalates.
According to calculations based on the Ideal Adsorption Solution Theory
(IAST), the maximum selectivity of the material for the CO 2 /CH 4 and CO 2 /N 2 mixtures is 11.5
and 56.0, respectively. These results suggest that LiNO 3 modification significantly enhances both the adsorption capacity
and the selectivity for CO 2 separation.
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高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2026
·
IF 3.5
Mi Yan,Cao Miao,Teng Cang,Xiangzhi Kong,Yan Zhang,Shuai Liu,Dan Wang,Ekkachai Kanchanatip
UiO-66 MOF was functionalized with dual ligands namely BDC-NH 2 and BDC-(OH) 2 . • Selective CO 2 /CH 4 adsorption were investigated at atmospheric and high pressures. • The highest CO 2 /CH 4 selectivity of 35.60 was achieved with 10%H-ZrMOF-A adsorbent. • CO 2 adsorption capacity of the adsorbent remained over 91.5% after five reuses. Selective CO 2 /CH 4 separation is essential for biogas valorization, yet conventional adsorbents typically face a trade-off between adsorption capacity and selectivity. In this work, a dual-ligand engineering strategy is implemented on UiO-66-NH 2 (ZrMOF-A) by co-incorporating 2,5-dihydroxyterephthalate (BDC-(OH) 2 ) to create a series of mixed-ligand MOFs denoted X %H-ZrMOF-A ( X = 5%–50% (mass)). The materials were synthesized via a solvothermal route and systematically characterized by N 2 physisorption, powder X-ray diffraction, FTIR spectroscopy, and SEM to elucidate structure-property relationships. Increasing hydroxyl content progressively modified surface area, pore volume, and morphology, with excessive BDC-(OH) 2 loading (>30% (mass)) inducing pronounced structural degradation. Among the series, 10%H-ZrMOF-A exhibited the most favorable balance between textural properties and functional site density, achieving a CO 2 uptake of 1.352 mmol·g –1 and a CO 2 /CH 4 selectivity of 35.60 at 100 kPa and 25 °C for a 40:60 CO 2 :CH 4 mixture predicted by IAST. Multi-model isotherm analysis identified the Freundlich and Elovich models as the most suitable descriptions of CO 2 adsorption, confirming a heterogeneous adsorption landscape arising from the coexistence of amine and hydroxyl sites. Complementary DFT calculations showed that dual functionalization strengthens CO 2 binding while weakening CH 4 interactions, consistent with the experimentally observed enhancement in selectivity. Pressure-dependent measurements revealed that high CO 2 /CH 4 selectivity at low pressures (≤100 kPa) diminishes at elevated pressures as non-selective pore filling becomes dominant, indicating that 10%H-ZrMOF-A is particularly suited for low-pressure biogas upgrading and post-combustion CO 2 capture. Five consecutive adsorption-desorption cycles demonstrated 91.5% capacity retention, confirming moderate short-term recyclability under mild thermal regeneration conditions. Download: Download high-res image (204KB) Download: Download full-size image
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高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2022
·
IF 5.518
Wenjia Luo,Zhenhua Niu,Peng Mu,Jian Li
Membrane separation systems have received extensive attention in the field of gas separation due to its low cost, high-efficiency and eco-friendly advantages. However, it is till challenging to break through the trade-off effect for a highly efficient membrane separation process. Herein, a high-performance CO 2 -philic MXene/PEG mixed matrix membrane is prepared by a simple vacuum filtration process. Excellent CO 2 permeance and selectivity in separation of the CO 2 /N 2 and CO 2 /CH 4 is shown for the as-prepared MXene/PEG (600) mixed matrix membrane because of CO 2 -philic property of the PEG and the nanochannels of the MXene . In permeation experiment, exceptional CO 2 permeance of 1626.99 GPU and ideal selectivity of 32.18 for CO 2 /N 2 and 27.84 for CO 2 /CH 4 , is exhibited, respectively, for 25 wt% MXene/PEG (600) mixed matrix membrane. This study provides a new strategy for design and fabrication of the CO 2 -philic MXene-based membrane with highly efficient separation of the CO 2 from natural gas and flue gas.
研究领域:
材料科学
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环境科学
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化学工程
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高影响因子
FUEL
·
2022
·
IF 8.035
Chengming Huang,Yiming Zhang,Dingmei Han,Binbin He,Xinyu Sun,Meiyu Liu,Yi Mei,Yun Zu
Ni-based catalysts using siliceous materials as the supports have suffered from two challenging issues of sintering and carbon deposition for dry reforming of methane (DRM), resulted from a weak metal-support interaction. Given these, a novel metal–acid bifunctional Ni@S-1 zeolite catalyst is tailored from the evolution of hydroxylated nickel phyllosilicates that are formed by subtly controlling the coordination environments of Ni precursor complexes in the silicalite-1 (S-1) zeolite. The developed Ni 0.44 @S-1 catalyst renders almost equivalent CH 4 and CO 2 conversions (85.1 % and 88.7 %), high H 2 /CO molar ratio (about 1) and superb long-term stability during 100 h with no activity loss at 750 °C with a WHSV of 100 L·g cat −1 ·h −1 , outperforming other control catalysts under investigation. Such superior catalytic behavior benefits from the synergy between highly uniform Ni nanoparticles (3–5 nm) confined in the micropores of zeolite and substantially formed Lewis acid sites due to coordinatively unsaturated Ni 2+ sites located at the reduced 2:1 nickel phyllosilicate, as revealed by detailed characterizations. Meanwhile, it further discloses that a benign balance between formation and elimination of “process carbon” species is responsible for improving the carbon resistance of catalyst during the DRM reaction. The present design broadens a new insight for the development of new Ni-based catalysts with simultaneous coking- and sintering-resistant for the DRM application.
研究领域:
催化化学
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材料科学
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
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IF 9
Yi Huang,Meng Cao,Lingfei Ye,Jie Liao,Haonan Wu,Lan Yi,Shangqing Chen,Fanpeng Cheng,Huijuan Guo,Liwei Cheng,Lijuan Shi,Qun Yi
Mixed matrix membranes (MMMs) incorporating porous fillers offer transformative potential for gas separations, yet their practical implementation is often hindered by interfacial defects and the inherent permeability–selectivity trade-off. Herein, we propose a covalent organic framework (COF) engineering strategy that integrates ionic functionalization with alkyl chain length modulation (C2, C8, C12) to fabricate high-performance 6FDA-DAM-based MMMs. By grafting bromoalkanes onto the pyridinic sites of TpDp COF, the resulting ionic COFs (iCOF TpDp–CnBr) synergistically eliminate interfacial voids through Br − -mediated electrostatic attraction and alkyl-dependent van der Waals interactions, while the bromide anions establish CO2-philic nanochannels via ion–quadrupole interactions. At 10 wt% loading, the 6FDA-DAM/TpDp–C8Br MMM achieves a CO 2 permeability of 363.7 Barrer and a CO 2 /CH 4 selectivity of 48.7, representing a 2.4-fold increase in permeability and a 2.7-fold enhancement in selectivity over the pristine polymer. This dual improvement transcends the 2008 Robeson upper bound, driven by optimized interfacial adhesion and tailored redistribution of free volume. Long-term stability tests (35 °C, 0.2 MPa) confirm structural integrity under the evaluated conditions. Density functional theory simulations reveal that the C8 alkyl chain minimizes interfacial energy by balancing steric hindrance and polymer–filler compatibility, establishing a charge–chain molecular design paradigm for next-generation membranes with promising application in natural gas purification.
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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高分子化学
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可持续能源
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高影响因子
危险品化学品经营许可证（带存储）