EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2024
·
IF 2.2
Mohan Chen,Yichao Wang,Ziwen Fan,Yue Wang,Zheng Niu,Jianping Lang
Graphical We prepared a series of fluorinated MOFs through the post- synthesis modification of the classic Zr-based MOF-808. The fluorinated alkane pores within MOFs can enhance the forces between the framework and C 2 H 2 , therefore, the difference in the adsorption capacity to C 2 H 2 and C 2 H 4 making it possible to effectively separate the C 2 H 2 /C 2 H 4 mixture at room temperature. The separation of ethylene (C 2 H 4 ) and acetylene (C 2 H 2 ) is challenging due to their similar molecular dimensions and boiling points, making conventional methods like cryogenic distillation and solvent extraction inefficient and environmentally harmful. Fluorinated metal-organic frameworks (MOFs) have been proven to be an effective material for the separation of C 2 H 4 and C 2 H 2. However, their direct synthesis is relatively expensive and challenging. In this study, we report a facile post-synthetic modification strategy to introduce fluorinated alkane pores into a zirconium-based MOF, MOF-808. The construction of fluorine-containing pores within the MOFs prefers adsorption for C 2 H 2 attributed to the interaction between the fluorine atoms and C 2 H 2 . This series of fluorinated MOFs demonstrates potential for gas separation processes, with the highest separation ratio reaching 2.67 (1 : 99) at 298 K. Breakthrough experiments for C 2 H 2 /C 2 H 4 mixtures confirmed that fluorinated MOF is capable of separating C 2 H 2 /C 2 H 4 , making it a potential candidate for industrial application. Moreover, the simplicity of the post-synthetic modification method suggests a viable strategy for the synthesis of fluorinated MOFs.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2025
·
IF 5.4
Qifan Yang,Haodong Xie,Xiang Ni,Li Liu,Yuan Xue,Yan Liu,Lei Wang,Hongjun Zhu
Adsorptive separation of C 2 H 2 from C 2 H 4 , which could deal with multi-steps for their similar kinetic diameter and physical properties, still poses a significant challenge. In this work, we prepared two metal cations (Co 2+ , Zn 2+ )-exchanged aluminosilicate FAU zeolites as an inorganic porous matrix, and grafted an organic zeolitic imidazole framework crystal layer to construct the inorganic–organic composites for gas separation process of C 2 H 4 among the mixed gas components. Such inorganic–organic porous composites can adsorb C 2 H 2 and hinder the large-sized C 2 H 4 . The Co-FAU@ZIF-8 composite was verified through breakthrough experiments and demonstrated a promising adsorptive volume of 1.46 mmol g −1 with an IAST selectivity of C 2 H 2 /C 2 H 4 of 5.6 at 298 K, respectively. Via powder X-ray diffraction crystallography and combined spectroscopy, we found that the exchanged metallic cation located at the accessible s 6 r , and served as the anchor point for the epitaxy of different crystals. Such tunable features ( i.e. , metallic centers and pore diameter) provide a potential pathway for the sub-sequential development of highly efficient adsorptive materials.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
AICHE JOURNAL
·
2015
·Vol. 61
·期 6
·2016-2027
·
IF 2.748
Xu Zhao,Qiwei Yang,Dan Xu,Zongbi Bao,Yi Zhang,Baogen Su,Qilong Ren,Huabin Xing
Ionic liquids (ILs) have been proposed as promising solvents for separating C 2 H 2 and C 2 H 4 , but screening an industrially attractive IL with high capacity from numerous available ILs remains challenging. In this work, a rapid screening method based on COSMO-RS was developed. We also present an efficient strategy to improve the C 2 H 2 capacity in ILs together with adequate C 2 H 2 /C 2 H 4 selectivity with the aid of COSMO-RS. The essence of this strategy is to increase molecular free volume of ILs and simultaneously enhance hydrogen-bond basicity of anions by introducing flexible and highly asymmetric structures, which is validated by a new class of tetraalkylphosphonium ILs featuring long-chain carboxylate anions. At 298.1 K and 1 bar, the solubility of C 2 H 2 in ILs reaches 0.476 mol/mol IL, very high for a physical absorption, with a selectivity of up to 21.4. The separation performance of tetraalkylphosphonium ILs to the mixture of C 2 H 2 /C 2 H 4 was also evaluated. © 2015 American Institute of Chemical Engineers AIChE J , 61: 2016–2027, 2015
研究领域:
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Jialang Hu,Yan Zhang,Mingyuan Jiang,Chao Xiong,Shenwei Chen,Jin Li,Xu Li,Ziyuan Zhu,Peng Hu,Hongbing Ji
Effective separation of acetylene/ethylene (C 2 H 2 /C 2 H 4 ) mixtures by adsorption is a challenging but green method given their similar molecular characters. An increasing number of metal-organic frameworks (MOFs) have addressed the diffusion-related challenges to achieve the separation, yet almost all of them just focus on diffusion rates and disregard the geometrical arrangement of adsorbed molecules which exerts important effects in boosting the diffusion behaviors. Herein, we now present a paradigm using an ultramicroporous zinc-MOF (Zn-MOF, referred to as 1 ) with assessable size of 3.4 × 3.3 Å 2 , as demonstrated by single-crystal and theoretical analysis, which realizes the effective separation of C 2 H 2 from its competitors. Static adsorption isotherms indicate that 1 possesses higher C 2 H 2 uptake of 28.4 cm 3 g −1 at 298 K and 0.1 bar, achieving a high IAST selectivity of 265 among the benchmark MOFs. Theoretical calculations reveal that C 2 H 2 molecules are grasped through multiple binding interactions and adsorbed in the pore surface rather than the center of the pore, thus forming C 2 H 2 tetramer through connecting four C 2 H 2 motifs. Further, time-dependent kinetic tests coupled with molecular dynamics confirm the faster diffusion behavior for C 2 H 2 , mainly attributing to unimpeded diffusion channel. Column breakthrough tests demonstrate that 1 can easily accomplish exclusive separation of C 2 H 2 from various binary ethane dehydrogenation (EDH) and senary non-oxidative coupling of methane (non-OCM) byproducts. Specially, structurally stable 1 can be readily synthesized utilizing inexpensive raw materials, yielding the cost of only $614 per kilogram. Accordingly, this work proposes a novel strategy of wall-trapped C 2 H 2 tetramer in MOF that can effectively promote the kinetic behavior through available diffusion channel, expecting to offer a new perspective and provide guidance for future research.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-9
·
IF 17.694
Liu Yuan,Liu Junhui,Xiong Hanting,Chen Jingwen,Chen Shixia,Zeng Zheling,Deng Shuguang,Wang Jun
Efficient adsorptive separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) or ethylene (C 2 H 4 ) is industrially important but challenging due to the identical dynamic diameter or the trace amount. Here we show an electrostatic potential compatible strategy in a nitroprusside-based Hofmann-type metal-organic framework, Cu(bpy)NP (NP = nitroprusside, bpy = 4,4’-bipyridine), for efficient C 2 H 2 separation. The intruding cyanide and nitrosyl groups in undulating one-dimensional channels induce negative electrostatic potentials for preferential C 2 H 2 recognition instead of open metal sites in traditional Hofmann-type MOFs. As a result, Cu(bpy)NP exhibits a 50/50 C 2 H 2 /CO 2 selectivity of 47.2, outperforming most rigid MOFs. The dynamic breakthrough experiment demonstrates a 99.9% purity C 2 H 4 productivity of 20.57 mmol g −1 from C 2 H 2 /C 2 H 4 (1/99, v / v ) gas-mixture. Meanwhile, C 2 H 2 can also be captured and recognized from ternary C 2 H 2 /CO 2 /C 2 H 4 (25/25/50, v/v/v ) gas-mixture. Furthermore, computational studies and in-situ infrared spectroscopy reveal that the selective C 2 H 2 binding arises from the compatible pore electro-environment generated by the electron-rich N and O atoms from nitroprusside anions.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2021
·
IF 3.498
Di-Ming Chen,Yin-Ping Zheng,Shao-Ming Fang
The selective separation of C 2 H 2 from C 2 H 4 is a very important process for downstream industrial production, and porous metal-organic frameworks (MOFs) have shown great potential for such an application due to their tunable pore surroundings and adjustable building blocks. In this study, a new microporous MOF formulated as {(Et 2 NH 2 )[In(TBOT)(2,3-FDA)](DEF)(H 2 O) 2 } n ( 1 , H 3 TBOT = 4,4′,4’’-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(oxy))tris(methylene))tribenzoic acid, 2,3-HFDA = 2,3-difluorobenzoic acid and DEF = N , N -diethylformamide) with 2-fold interpenetrated network and 1D fluorine-decorated pores has been prepared via using an acid-acid mixed-ligand strategy. The activated complex 1 (named as 1a ) demonstrates apparently higher C 2 H 2 uptake than C 2 H 4 around room temperature , resulting in its relative high C 2 H 2 /C 2 H 4 (v:v = 1:99) IAST (Ideal Adsorbed Solution Theory) selectivity of 10.3 at 298 K and 1 bar. Furthermore, the GCMC (grand canonical Monte Carlo) simulation results indicate that the 2,3-FDA moieties serve as preferential binding sites for C 2 H 2 via the multipoint F 2 ⋯H–C C–H⋯F 2 interactions, implying the feasibility of the mixed-ligand approach for building porous MOFs with the targeted applications.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2019
·Vol. 25
·期 38
·9045-9051
·
IF 5.16
Lingchang Jiang,Pengyuan Wang,Meiping Li,Panpan Zhang,Jialu Li,Jia Liu,Yanhang Ma,Hao Ren,Guangshan Zhu
Graphical Lapping it up : A thermally and chemically stable, crystalline polyimide porous organic framework, was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride with triangular 1,3,5-tris(4-aminophenyl)benzene. This material is capable of selective adsorption of C 2 H 2 over C 2 H 4 and CO 2 over N 2 (see figure). Utilization of porous materials for gas capture and separation is a hot research topic. Removal of acetylene (C 2 H 2 ) from ethylene (C 2 H 4 ) is important in the oil refining and petrochemical industries, since C 2 H 2 impurities deactivate the catalysts and terminate the polymerization of C 2 H 4 . Carbon dioxide (CO 2 ) emission from power plants contributes to global climate change and threatens the survival of life on this planet. Herein, 2D crystalline polyimide porous organic framework PAF-120, which was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular 1,3,5-tris(4-aminophenyl)benzene, showed significant thermal and chemical stability. Low-pressure gas adsorption isotherms revealed that PAF-120 exhibits good selective adsorption of C 2 H 2 over C 2 H 4 and CO 2 over N 2 . At 298 K and 1 bar, its C 2 H 2 and CO 2 selectivities were predicted to be 4.1 and 68.7, respectively. More importantly, PAF-120 exhibits the highest selectivity for C 2 H 2 /C 2 H 4 separation among porous organic frameworks. Thus PAF-120 could be a suitable candidate for selective separation of C 2 H 2 over C 2 H 4 and CO 2 over N 2 .
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Jia-Nuo Li,Ding Chen,Yunli Wang,Jia Li,Yuqiao Chai,Xunwen Xiao,Xing Li,Jin-Peng Xue
Multi-interpenetrated metal–organic frameworks (MOFs) have exhibited excellent performance in selective adsorption due to the variable post-interspersed flexibility, but the design and control remain challenging. Herein, two anthracene-based ligands, 4,4′-(anthracene-9,10-diyl)dibenzoic acid (H2L1) and 9,10-di(pyridin-4-yl)anthracene (L2), are used to construct a new three-dimensional 6-fold interpenetrated MOF [Zn(L1)(L2)]n (NBU-X1), which exhibits multiple C–H···π interactions that enhance the structural rigidity, thereby entangling with a C2H2/C2H4 separation performance. In this material, the incorporation of abundant anthracene rings within the framework not only partitions and restricts the pore window size to a quasi-double pore but also stabilizes it through host–host interactions. The structural stability upon heating or guest displacement/removal has been investigated by single-crystal X-ray diffraction and in situ variable-temperature powder X-ray diffraction, in contrast to the extreme flexibility of most multi-interpenetrated MOFs. The performance of purifying C2H4 from C2H2/C2H4 mixtures has been proved by dynamic breakthrough tests.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）