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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Separation of ethylene glycol and ethylene glycol diacetate azeotropic mixture with a heterogeneous extraction distillation process

Wei Chen,Yan Ding,Fang Wang,Zhixia Xu,Qing Ye,Jinlong Li,Patrice Paricaud

The vapor-liquid equilibria of binary mixtures of ethylene glycol diacetate (EGDA) + o-chlorotoluene (OCT) and EGDA + cyclohexylbenzene (CHB), and the liquid-liquid equilibria (LLE) in ternary mixtures of ethylene glycol (EG) + EGDA + o-chlorotoluene and EG + EGDA + cyclohexylbenzene are measured in this work. The new data have been described with the NRTL thermodynamic model. The heterogeneous extractive distillation and liquid-liquid phase separation process for the investigated systems are then simulated using the Aspen Plus software and the adjusted thermodynamic model. The influence of key process parameters such as the ratio of solvent flow rate to feed flowrate, the plate number and the reflux ratio on the separation process are analyzed in detail, and the optimal process parameters are determined. An economic and environmental study of the process is then performed. It is found that the two extractants (o-chlorotoluene and cyclohexylbenzene) can achieve a good EG + EGDA azeotrope separation. The purities of both EG and EGDA products are greater than 99.50 wt% in the two processes. The predicted selectivity obtained with o-chlorotoluene is higher than the one obtained with cyclohexylbenzene process. However, the cyclohexylbenzene process is found to be was more environmentally friendly, and the utility costs and CO 2 emissions of are lower. This work brings new insights in the design and optimization for the separation of EG and EGDA azeotropic mixtures.

研究领域: 化学工程 · 过程系统工程 · 热力学 · 环境工程
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Fabrication of hierarchically porous University of Oslo-66@silica shell-core stationary phase by phosphoric acid etching strategy for enhanced separation performance in liquid chromatography

Yang Liu,Jian Li,Jiawei Liu,Changwei Tang,Quan Bai

Metal-organic frameworks (MOFs) are promising packing materials in liquid chromatography, but their micropore character extremely prevents the separation performance. Herein, we proposed an acidic etching strategy to fabricate a hierarchically porous University of Oslo-66 (HP-UiO-66) coated silica shell-core composite by using phosphoric acid as an etchant. The prepared composite, namely HP-UiO-66@silica-PA, was characterized by SEM, TEM, FT-IR, and N 2 -adsorption–desorption isotherms, demonstrating the generation of mesopores in HP-UiO-66 shell with pore width ranging in 4–5 nm. The chromatographic performance of HP-UiO-66@silica-PA-1 (etched by 1 mL phosphoric acid for 2 h) as HPLC stationary phase was evaluated in reversed-phase mode, and the separations of three groups of small solutes were studied and compared with the microporous UiO-66@silica (MP-UiO-66@silica) column. The results proved the obviously improved performances with narrower peak width, better resolution, and higher symmetry were achieved by the HP-UiO-66@silica-PA-1 column. The faster diffusion and mass transfer kinetics in the HP-UiO-66 shell signally reduce the plate height and improve the column efficiency. Specifically, the plate number of o -xylene was 18,442 plates m −1 , which was about 18.5 times higher than that on the MP-UiO-66@silica column (993 plates m −1 ). Furthermore, good repeatability and reproducibility with RSDs of both retention time and peak area less than 0.5 % confirmed the high stability and outstanding reliability of the HP-UiO-66@silica-PA-1 column. This study demonstrates that the phosphoric acid etching strategy is simple, mild, and controllable to fabricate hierarchically porous MOFs-based stationary phase for enhancing the HPLC separation performance.

研究领域: 分析化学 · 材料科学 · 色谱
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ANALYTICA CHIMICA ACTA · 2015 · IF 4.513

Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

Youhong Ai,Faqiong Zhao,Baizhao Zeng

A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N -methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100   μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048   μg/L (S/N   =   3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% ( n   =   5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes.

研究领域: 分析化学 · 材料科学
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ANALYTICAL CHEMISTRY · 2011 · IF 5.874

Metal–Organic Framework MIL-101(Cr) for High-Performance Liquid Chromatographic Separation of Substituted Aromatics

Cheng-Xiong Yang,Xiu-Ping Yan

The diverse structures and pore topologies, accessible cages and tunnels, and high surface areas make metal–organic frameworks attractive as novel media in separation sciences. Here we report the slurry-packed MIL-101(Cr) column for high-performance liquid chromatographic separation of substituted aromatics. The MIL-101(Cr) packed column (5 cm long × 4.6 mm i.d.) offered high-resolution separation of ethylbenzene (EB) and xylene, dichlorobenzene and chlorotoluene isomers, and EB and styrene. The typical impurities of toluene and o-xylene in EB and styrene mixtures were also efficiently separated on the MIL-101(Cr) packed column. The column efficiencies for EB, m-dichlorobenzene, and m-chlorotoluene are 20000, 13000, and 10000 plates m–1, respectively. The relative standard deviation for five replicate separations of the substituted aromatics was 0.2–0.7%, 0.9–2.9%, 0.5–2.1%, and 0.6–2.7% for the retention time, peak area, peak height, and half peak width, respectively. The MIL-101(Cr) offered high affinity for the ortho-isomer, allowing fast and selective separation of the ortho-isomer from the other isomers within 3 min using dichloromethane as the mobile phase. The effects of the mobile phase composition, injected sample mass, and temperature were investigated. The separation of xylene, dichlorobenzene, and chlorotoluene on MIL-101(Cr) was controlled by entropy change, while the separation of EB and styrene on MIL-101(Cr) was governed by enthalpy change.

研究领域: 分析化学 · 材料科学
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JOURNAL OF CHROMATOGRAPHY A · 2012 · IF 4.531

Exploring reverse shape selectivity and molecular sieving effect of metal-organic framework UIO-66 coated capillary column for gas chromatographic separation

Na Chang,Xiu-Ping Yan

Metal-organic frameworks (MOFs) which offer a variety of topologies, porous networks and high surface areas are promising and have potential for the applications of specific adsorption, isomerization, catalysis and separation. UIO-66 is the first MOF that has been observed to have reverse shape selectivity. However, such reverse shape selectivity of MOFs has never been explored for capillary gas chromatographic separation. Here we report the fabrication of MOF UIO-66 coated capillary column and exploration of the reverse shape selectivity and molecular sieving effect of such column for capillary gas chromatographic separation of alkane isomers and benzene homologues with excellent selectivity and precision. The adsorption enthalpies and entropies on the interaction between hydrocarbons and UIO-66 were measured to illustrate the energy effect on the separation of alkane isomers and benzene homologues on the UIO-66 coated capillary column. UIO-66 coated capillary column gave preferential retention of branched alkane isomers over their linear isomer, showing reverse shape selectivity, making UIO-66 coated capillary column attractive for capillary gas chromatographic separation of alkane isomers. iso -Propylbenzene (branched) eluted after n -propylbenzene on the UIO-66 coated capillary column again shows reverse shape selectivity. However, much bulkier 1,3,5-trimethylbenzene eluted earlier than n -propylbenzene and iso -propylbenzene on the UIO-66 coated capillary column, exhibiting molecular sieving effect. The combination of reverse shape selectivity with molecular sieving effect makes the UIO-66 coated capillary column promising for the separation of structural isomers.

CAS / MDL: 95-49-8 95-50-1
研究领域: 化学 · 材料科学
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Green and Controlled Synthesis of Copper-Based Tryptophan Flower-like Chiral Metal-Organic Framework for Enantioselective Recognition and Volatile Organic Compound Separation

Jinhua Xu,Minghui Tang,Jinyu Zhang,Wenmin Zhang,Shiye Xie,Lan Zhang

This study reports the synthesis and application of a flower-like chiral metal-organic framework (CMOF) based on copper ions and tryptophan (Cu(Trp)-CMOF). The Cu(Trp)-CMOF was successfully synthesized at room temperature through a facile method with hexadecyl trimethyl ammonium bromide (CTAB) as a structure-directing agent. The material exhibits a flower-like morphology with hierarchical porosity and well-defined crystallinity in the monoclinic P2 1 /c space group. Comprehensive characterization revealed that different optical configurations ((R)-type, (S)-type, and (RS)-type) could be selectively obtained by controlling the chirality of tryptophan ligands. The synthesized CMOFs demonstrated excellent performance in two key applications: colorimetric recognition of amino acid enantiomers and separation of volatile organic compounds (VOCs). When used as a chromatographic stationary phase, the CMOF significantly enhanced the separation of challenging structural isomers, particularly improving the resolution (R S ) of xylene isomers (R S from 1.03 to 2.62) and ethyltoluene isomers (R S from 4.83 to 9.23) compared to conventional columns. This work provides new insights into the design and application of CMOFs for chiral separation and recognition.

研究领域: 材料科学 · 化学
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ANALYST · 2011 ·Vol. 137 ·期 1 ·133-139 · IF 3.913

High-performance liquid chromatographic separation of position isomers using metal–organic framework MIL-53(Al) as the stationary phase

Cheng-Xiong Yang,Shan-Shan Liu,He-Fang Wang,Shan-Wei Wang,Xiu-Ping Yan

Metal–organic framework MIL-53(Al) was explored as the stationary phase for high-performance liquid chromatographic separation of position isomers using a binary and/or polar mobile phase. Baseline separations of xylene, dichlorobenzene, chlorotoluene and nitrophenol isomers were achieved on the slurry-packed MIL-53(Al) column with high resolution and good precision. The effects of mobile phase composition, injected sample mass and temperature were investigated. The separation of xylene, dichlorobenzene, chlorotoluene and nitrophenol isomers on MIL-53(Al) were controlled by entropy change.

研究领域: 化学 · 分析化学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Low-temperature processed cross-linkable hole transport layer for efficient and stable perovskite solar cells

Yikun Zhang,Hongli Liu,Shirong Wang,Huayu Bao,Xianggao Li

To the best of our knowledge, poor environment stability is the main challenge for perovskite solar cells (PSCs). In this study, cross-linked hole transport layer (HTL) is built on perovskite crystal to guarantee the operation stability of mesoporous PSCs for the first time. Here, N,N' -di-p-tolyl- N,-N' -bis(4-vinylphenyl)-[1,1′-biphenyl]-4,4′-diamine (V-p-TPD) was applied as a hole-transportable polymerizable monomer with the assistance of ultraviolet photoinitiator 4-octyloxydiphenyliodonium hexafluoroantimonate (OPPI). Cross-linking process is conducted at a distinctly low temperature of only 100 °C by adjusting the V-p-TPD: OPPI ratio to 10:1, which is tolerable for the active black phase of perovskite. The resultant cross-linked V-p-TPD film is qualified with a high cross-linking degree of 99%, a high hole mobility of 3.84 × 10 −4 cm 2 V −1 s −1 and a hydrophobic surface with wetting angle of 94.6°. Mesoporous PSCs based on the obtained cross-linked HTL achieved a tremendous Power conversion efficiency (PCE) of 18.49%, which represents the state-of-the-art records of mesoporous PSCs with cross-linkable HTL. PCE of the unpackaged device can remain 88% of the initial value after 30 d in an atmospheric environment with a relative humidity of 60 ± 5%, and maintain 86% of the initial PCE after 200 h in 65 ± 2 °C argon atmosphere. This work presents a low-temperature processing strategy for the preparation of cross-linked HTL layer, which does favor to the stable and efficient energy harvesting application.

研究领域: 材料科学 · 能源技术
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TALANTA · 2020 · IF 5.339

Covalent coupling fabrication of microporous organic network bonded capillary columns for gas chromatographic separation

Xue Li,Yuan-Yuan Cui,Cheng-Xiong Yang

Microporous organic networks (MONs) have shown great promise in separation science recently. Exploring novel, simple and convenient strategy to fabricate MONs coated capillary columns for gas chromatography (GC) still remains challenging but desirable for the development of MONs in chromatographic separation. To extend the potential application of MONs in separation science and to further develop novel method for the fabrication of MONs-based capillary columns, here we demonstrate a novel covalent coupling strategy to fabricate uniform MONs bonded capillary columns for GC separation of position isomers and hydrocarbons. The bare capillary column was firstly modified with (3-bromopropyl)trimethoxysilane to provide bromine sites for coupling with alkynyl monomers . The amino- and hydroxyl-functionalized MONs (MON-NH 2 and MON-OH) were then directly grown onto the inner wall of the brominated capillary columns via the covalent coupling between bromine and alkynyl groups. The uniform MON-NH 2 and MON-OH bonded capillary columns were obtained and showed good resolution for GC separation of dichlorobenzene , chlorotoluene, bromotoluene, and propylbenzene position isomers and many other hydrocarbons including linear alkanes, alkylbenzenes , pinene isomers, cyclohexane and benzene, ketones and aldehydes. The MONs bonded capillary columns also owned good lifetime and precision for dichlorobenzene isomers with the relative standard deviations (RSDs) of 0.2–0.3%, 1.2–2.1%, and 1.7–2.5% for retention time, peak height and peak area, respectively. In addition, the fabricated MON-NH 2 and MON-OH bonded capillary columns offered better resolution than commercial InertCap-1, InertCap-5, InertCap-1701 and InertCap-WAX capillary columns for the separation of chlorotoluene and bromotoluene position isomers. These results revealed the feasibility of covalent coupling strategy to fabricate MONs-based stationary phases in GC, highlighting the potential of MONs in separation science.

研究领域: 分析化学 · 分离科学 · 材料科学
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TALANTA · 2015 · IF 3.545

Facile fabrication of ionic liquid doped polycarbazole coating for the headspace solid-phase microextraction of some environmental pollutants

Yuanyuan Feng,Mian Wu,Faqiong Zhao,Baizhao Zeng

A novel polycarbazole (PCz)–ionic liquid (IL, i.e. 1-hydroxyethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [HOEMIm][NTf 2 ]) composite coating (PCz-IL) was fabricated by electrodeposition. The IL could facilitate the electrodeposition of poor-conductive PCz and a more porous coating was obtained. The composite coating exhibited enhanced extraction capacity for some environmental pollutants (i.e. o-chlorotoluene, p-bromotoluene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene), as they could interact through π-π and hydrophobic interactions. Compared with [HOEMIm][NTf 2 ] coated fiber, some other PCz-IL fibers (here IL=1-hydroxyethyl-3-methylimidazolium hexafluorophosphate and 1-methyl-3-octylimidazolium hexafluorophosphate) and commercial fibers (i.e. polydimethylsiloxane and polyacrylate), the PCz-IL fiber showed better performance. It was used for the determination of the environmental pollutants by coupling with gas chromatography, the limits of detection were 47.8–65.9   ng   L −1 under the optimized conditions and the linear ranges were 0.1–500   μg   L −1 with correlation coefficients above 0.9947 for different compounds. The relative standard deviations (RSDs) were 3.4–4.6% for five successive extractions with single fiber, and the RSDs for inter-fiber were 6.5–10.4% ( n =5). The fiber was successfully applied to the detection of real samples and the recoveries for standards added were 88.6–108.8% with RSDs below 9.7%.

研究领域: 分析化学 · 环境科学
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

General Two-Step Method for the Fabrication of Covalent-Organic Framework-Bound Open-Tubular Capillary Columns for High-Resolution Gas Chromatography Separation of Isomers

Wen-Chao Deng,Hai-Long Qian,Cheng Yang,Shu-Ting Xu,Xiu-Ping Yan

Covalent organic frameworks (COFs) are promising as stationary phases for gas chromatography (GC). The successful anchoring of COFs to the inner walls of the capillary with good uniformity is an important prerequisite to ensure the excellent separation performance of columns. However, current methods for the fabrication of COF-based capillary columns cannot always meet this requirement when faced with different COFs, which hampers the further development of COF-based GC stationary phases. Here, we show a general two-step method for the fabrication of COF-bound capillary column. The first step enables the formation of uniform amorphous polymer layer on the inner walls of capillary, while the second step allows the facile transformation of the amorphous polymer layer into a highly crystalline COF layer. COF-bound capillary columns with different framework structures were fabricated successfully by the developed two-step method. Impressively, the COF layers bound on the inner walls of these capillary columns showed good uniformity and high crystallinity. More importantly, as an example, the fabricated Tab-DHTA-bound capillary column showed good resolution (R > 1.5) and high column efficiency (700–39,663 plates m–1) for the tested isomers of ethylbenzene, xylene, dichlorobenzene, chlorotoluene, pinene, 1,3-dichloropropene, and propylbenzene with good precision (RSD, run-to-run, n = 5) (retention time, 0.2–0.6%; peak area, 0.5–1.1%; and peak height, 0.5–1.4%). In general, the fabricated Tab-DHTA-bound capillary column exhibited better performance for the separation isomers than commercial columns DB-5 and HP-FFAP. These results indicate that the two-step method is an efficient way to fabricate the COF-bound capillary column with excellent separation performance.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Trifluoromethyl-Functionalized 2D Covalent Organic Framework for High-Resolution Separation of Isomers

Tian-Tian Ma,Cheng Yang,Hai-Long Qian,Piming Ma,Tianxi Liu,Xiu-Ping Yan

Development of novel functional materials for effective isomer separation is of great significance in environmental science, chemical industry, and life science due to the different functions of isomers. However, the similar physicochemical properties of isomers make their separation greatly challenging. Here, we report the fabrication of trifluoromethyl-functionalized 2D covalent organic framework (COF) TpTFMB with 2,2′-bis(trifluoromethyl)benzidine (TFMB) and 1,3,5-triformylphloroglucinol (Tp) for the separation of isomers. TpTFMB was in situ-grown on the inner surface of a capillary for the high-resolution separation of isomers. The introduction of hydroxyl and trifluoromethyl functional groups with uniform distribution in 2D COFs is a powerful tactic to endow TpTFMB with various functions such as hydrogen bonding, dipole interaction, and steric effect. The prepared TpTFMB capillary column enabled the baseline separation of positional isomers such as ethylbenzene and xylene, chlorotoluene, carbon chain isomers such as butylbenzene and ethyl butanoate, and cis–trans isomers 1,3-dichloropropene. The hydrogen-bonding, dipole, and π–π interactions as well as the structure of COF significantly contribute to the isomer separation. This work provides a new strategy for designing functional 2D COFs for the efficient separation of isomers.

研究领域: 材料科学 · 化学工程 · 环境科学
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