基于含N有机配体的MOFs用于C2H6/C2H4吸附分离性能的研究

祁超录; 王丽; 杨江峰; 李晋平

doi:10.11949/0438-1157.20260553

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基于含N有机配体的MOFs用于C₂H₆/C₂H₄吸附分离性能的研究

分离工程 | 更新时间：2026-07-15

- 基于含N有机配体的MOFs用于C₂H₆/C₂H₄吸附分离性能的研究
- Study of C₂H₆/C₂H₄ adsorption and separation performance using MOFs based on nitrogen-containing organic ligands
- 化工学报 2026年
- 作者机构：
  
  1.太原理工大学化学与化工学院，山西太原 030024
  2.怀柔实验室山西研究院，山西太原 030032
- 作者简介：
  
  祁超录（2000—），女，硕士研究生，2290318647@qq.com
  王丽（1994—），女，博士，讲师，wangli05@tyut.edu.cn
  杨江峰（1982—），男，博士，教授，yangjiangfeng@tyut.edu.cn
- 基金信息：
  
  国家自然科学青年基金项目(22308238);山西省青年科学基金项目(202403021212044)
- DOI：10.11949/0438-1157.20260553
  中图分类号： TQ 028.1
- 收稿：2026-04-17，
  
  修回：2026-07-08，
  
  录用：2026-07-15，
- 稿件说明：
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祁超录, 王丽, 杨江峰, 等. 基于含N有机配体的MOFs用于C₂H₆/C₂H₄吸附分离性能的研究[J/OL]. 化工学报, 2026. DOI: 10.11949/0438-1157.20260553.

QI Chaolu, WANG Li, YANG Jiangfeng, et al. Study of C₂H₆/C₂H₄ adsorption and separation performance using MOFs based on nitrogen-containing organic ligands[J/OL]. CIESC Journal, 2026. DOI: 10.11949/0438-1157.20260553.
祁超录, 王丽, 杨江峰, 等. 基于含N有机配体的MOFs用于C₂H₆/C₂H₄吸附分离性能的研究[J/OL]. 化工学报, 2026. DOI: 10.11949/0438-1157.20260553. DOI：

QI Chaolu, WANG Li, YANG Jiangfeng, et al. Study of C₂H₆/C₂H₄ adsorption and separation performance using MOFs based on nitrogen-containing organic ligands[J/OL]. CIESC Journal, 2026. DOI: 10.11949/0438-1157.20260553. DOI：

摘要

作为现代石油化学工业的核心过程之一，乙烷与乙烯的有效分离具有重要的工业应用价值。利用含氮杂环化合物TCPP作为配体，采用溶剂热法成功合成了PPF-1-Zn和金属取代的同构钴基材料PPF-1-Co。采用PXRD、TGA和77 K下的N

吸脱附等温线对材料的结构与孔性能进行了系统表征。测试了两种材料对乙烷和乙烯单组分气体的吸附性能，并进行了选择性和吸附热的计算。两种材料对乙烷的吸附量均高于乙烯，表现出对乙烷的优先吸附特性，在298 K和1 bar条件下，C

选择性均为1.64。吸附热计算表明，PPF-1-Zn的C

吸附热较低，为25.9 kJ/mol，有利于吸附剂再生。混合气体穿透实验表明，PPF-1-Zn具有良好的C

分离性能和稳定性。密度泛函理论（DFT）计算表明，配体中的N原子是主要的气体吸附位点。

Abstract

As one of the core processes in the modern petrochemical industry

the efficient separation of ethan

e and ethylene holds significant industrial application value. PPF-1-Zn

using the N-heterocyclic compound TCPP as the ligand

and its metal-substituted

isostructural cobalt-based counterpart

PPF-1-Co

were successfully synthesized via a solvothermal method. Their crystal structures and porosity were systematically characterized by powder X-ray diffraction (PXRD)

thermogravimetric analysis (TGA)

and N

sorption isotherms at 77 K. The single-component gas adsorption performance of both materials for ethane and ethylene was evaluated

and their selectivities and heats of adsorption were calculated. Both materials exhibited higher adsorption capacities for ethane than for ethylene

demonstrating a preferential adsorption towards ethane with a C

selectivity of 1.64 at 298 K and 1 bar. The adsorption heat of C

on PPF-1-Zn is relatively low (25.9 kJ/mol)

which facilitates adsorbent regeneration. Dynamic mixed-gas breakthrough experiments demonstrate that PPF-1-Zn exhibits reasonable C

separation performance and stability. Density functional theory (DFT) calculations indicate that the N atom in the ligand is the primary gas adsorption site.

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references

Peng B S , Liu Z Y , Ma X Y , et al . A cation-functionalized layer for ethylene electrosynthesis via CO reduction paired with H 2 oxidation in a pure-water-fed solid-state electrolyser [J ] . Nature Energy , 2026 , 11 ( 5 ): 689 - 698 .

杨东晓 . 双吡啶基金属有机框架材料的合成及其乙烯吸附分离研究 [D ] . 太原 : 太原理工大学 , 2024 .

Yang D X . Synthesis of bipyridine-based metal-organic framework materials for ethylene adsorption and separation studies [D ] . Taiyuan : Taiyuan University of Technology , 2024 .

Anwar F , Khaleel M , Wang K A , et al . Selectivity tuning of adsorbents for ethane/ethylene separation: a review [J ] . Industrial & Engineering Chemistry Research , 2022 , 61 ( 34 ): 12269 - 12293 .

Jiang Y , Jia S J , Liu X Q , et al . Selective adsorption of ethane over ethylene through a metal–organic framework bearing dense alkyl groups [J ] . Separation and Purification Technology , 2022 , 295 : 121330 .

Peng H P , Peng Y C , Xue F , et al . Stable, high-yield ethylene production from vapor-assisted light-driven ethane dehydrogenation [J ] . Journal of the American Chemical Society , 2026 , 148 ( 5 ): 5713 - 5721 .

GB/T 7715—2014 工业用乙烯 [S ] .

GB/T 7715—2014 Ethylene for industrial use—Specification [S ] .

Jiang H C , Li S M , Ni Q L , et al . Pore engineering in double-wall MOFs through immobilizing functional bonding sites for boosting efficient ethane/ethylene separation [J ] . Separation and Purification Technology , 2025 , 363 : 132033 .

Duan C P , Chen R D , Li J Q , et al . Ethane-selective metal-organic frameworks for one-step purification of ethylene [J ] . Chemical Communications , 2026 , 62 ( 1 ): 16 – 30 .

Mu X T , Ouyang Y S , Pei L M , et al . Control of pore environment in highly porous carbon materials for C 2 H 6 /C 2 H 4 separation with exceptional ethane uptake [J ] . Materials Today Chemistry , 2022 , 24 : 100856 .

Sholl D S , Lively R P . Seven chemical separations to change the world [J ] . Nature , 2016 , 532 ( 7600 ): 435 - 437 .

Zhang X , Wang J X , Li L B , et al . A rod-packing hydrogen-bonded organic framework with suitable pore confinement for benchmark ethane/ethylene separation [J ] . Angewandte Chemie International Edition , 2021 , 60 ( 18 ): 10304 - 10310 .

Wen H M , He Z J , Fei Y W , et al . A V-shaped microporous metal-organic framework with multiple binding sites for highly efficient ethane/ethylene separation [J ] . Nano Research , 2026 , 19 ( 7 ): 94908523 .

Chang Y J , Huang H L , Zhu H J , et al . Robust carbazole-based covalent triazine frameworks with defective ultramicropore structure for efficient ethane-selective ethane-ethylene separation [J ] . Chemical Engineering Journal , 2022 , 427 : 131726 .

Zhang T , Cao J W , Zhang S Y , et al . General pore features for one-step C 2 H 4 production from a C2 hydrocarbon mixture [J ] . Chemical Communications , 2022 , 58 ( 32 ): 4954 - 4957 .

Yang S Q , Hu T L . Reverse-selective metal–organic framework materials for the efficient separation and purification of light hydrocarbons [J ] . Coordination Chemistry Reviews , 2022 , 468 : 214628 .

Wu Y Q , Weckhuysen B M . Separation and purification of hydrocarbons with porous materials [J ] . Angewandte Chemie International Edition , 2021 , 60 ( 35 ): 18930 - 18949 .

Zheng Y Y , Miao G , Yang C T , et al . Fast size-sieving separation of C 2 H 4 /C 2 H 6 by pore engineering of scalable carbon molecular sieve granules [J ] . Chemical Engineering Science , 2026 , 320 : 122640 .

Wang J X , Gu X W , Lin Y X , et al . A novel hydrogen-bonded organic framework with highly permanent porosity for boosting ethane/ethylene separation [J ] . ACS Materials Letters , 2021 , 3 ( 5 ): 497 - 503 .

Yuan W H , Zhang X T , Li L . Synthesis of zeolitic imidazolate framework-69 for adsorption separation of ethane and ethylene [J ] . Journal of Solid State Chemistry , 2017 , 251 : 198 - 203 .

Yi M , Wang S , Li S F , et al . Superhydrophobic molecular selector for efficient separation of ethane over ethylene under dry and humid conditions [J ] . Journal of the American Chemical Society , 2025 , 147 ( 16 ) : 13592 - 13600 .

Bindra A K , Wang D D , Zhao Y L . Metal–organic frameworks meet polymers: from synthesis strategies to healthcare applications [J ] . Advanced Materials , 2023 , 35 ( 40 ): 2300700 .

Chen Y W , Qiao Z W , Wu H X , et al . An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene [J ] . Chemical Engineering Science , 2018 , 175 : 110 - 117 .

Zeng H , Xie X J , Xie M , et al . Cage-interconnected metal–organic framework with tailored apertures for efficient C 2 H 6 /C 2 H 4 separation under humid conditions [J ] . Journal of the American Chemical Society , 2019 , 141 ( 51 ): 20390 - 20396 .

Jiang Z Z , Fan L H , Zhou P , et al . An aromatic-rich cage-based MOF with inorganic chloride ions decorating the pore surface displaying the preferential adsorption of C 2 H 2 and C 2 H 6 over C 2 H 4 [J ] . Inorganic Chemistry Frontiers , 2021 , 8 ( 5 ): 1243 - 1252 .

Ma Y Y , Shi W J , Wang G D , et al . Enhancing ethane/ethylene separation performance through the amino-functionalization of ethane-selective MOF [J ] . Chinese Chemical Letters , 2025 , 36 ( 3 ): 109729 .

Xu Y X , Xu J B , Yang C . Molecule design of effective C 2 H 4 /C 2 H 6 separation membranes: From 2D nanoporous graphene to 3D AHT zeolite [J ] . Journal of Membrane Science , 2020 , 604 : 118033 .

Sun Y W , Hu S , Yan J H , et al . Oriented ultrathin π-complexation MOF membrane for ethylene/ethane and flue gas separations [J ] . Angewandte Chemie , 2023 , 135 ( 43 ): e202311336 .

Pirdadeh Beiranvand R , Ovaysi S . Mechanochemical synthesis of Cu(I)-MOF-74 for improved ethylene/ethane separation [J ] . ACS Omega , 2026 , 11 ( 1 ): 1236 - 1244 .

Liu X W , Kong D X , Tong G Y , et al . Microsize and environment regulation of Mn-based MOF for inverse ethane/ethylene separation [J ] . Separation and Purification Technology , 2026 , 382 : 136172 .

Mukherjee D , Pal S C , Wang J X , et al . Two-in-one flexible metal–organic framework: one-step C 2 H 4 purification via inverse C 2 H 6 –C 2 H 4 and C 2 H 2 –CO 2 separations [J ] . Journal of the American Chemical Society , 2025 , 147 ( 32 ): 29255 - 29270 .

Gücüyener C , van den Bergh J , Gascon J , et al . Ethane/ethene separation turned on its head: selective ethane adsorption on the metal–organic framework ZIF-7 through a gate-opening mechanism [J ] . Journal of the American Chemical Society , 2010 , 132 ( 50 ): 17704 - 17706 .

Lin R B , Wu H , Li L B , et al . Boosting ethane/ethylene separation within isoreticular ultramicroporous metal–organic frameworks [J ] . Journal of the American Chemical Society , 2018 , 140 ( 40 ): 12940 - 12946 .

Liao P Q , Zhang W X , Zhang J P , et al . Efficient purification of ethene by an ethane-trapping metal-organic framework [J ] . Nature Communications , 2015 , 6 : 8697 .

Li L B , Lin R B , Krishna R , et al . Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites [J ] . Science , 2018 , 362 ( 6413 ): 443 - 446 .

Cui W G , Hu T L , Bu X H . Metal–organic framework materials for the separation and purification of light hydrocarbons [J ] . Advanced Materials , 2020 , 32 ( 3 ): 1806445 .

You R M , Ma Y X , Yu C , et al . Highly selective ethylene/ethane separation in MOF composites through pore contraction and particle size enlargement strategy [J ] . Small Methods , 2025 , 9 ( 7 ): 2402061 .

Lv D F , Zhou P J , Xu J H , et al . Recent advances in adsorptive separation of ethane and ethylene by C 2 H 6 -selective MOFs and other adsorbents [J ] . Chemical Engineering Journal , 2022 , 431 : 133208 .

Wang G D , Krishna R , Li Y Z , et al . Boosting ethane/ethylene separation by MOFs through the amino-functionalization of pores [J ] . Angewandte Chemie , 2022 , 134 ( 48 ): e202213015 .

Song C H , Zheng F , Liu Y , et al . Spatial distribution of nitrogen binding sites in metal-organic frameworks for selective ethane adsorption and one-step ethylene purification [J ] . Angewandte Chemie , 2023 , 135 ( 51 ): e202313855 .

Zhang Y P , Lv D F , Chen J Y , et al . Preferential adsorption of ethane over ethylene on a Zr-based metal–organic framework: impacts of C–H⋯N hydrogen bonding [J ] . New Journal of Chemistry , 2021 , 45 ( 18 ): 8045 - 8053 .

Choi E Y , Wray C A , Hu C H , et al . Highly tunable metal–organic frameworks with open metal centers [J ] . CrystEngComm , 2009 , 11 ( 4 ): 553 - 555 .

Myers A L , Prausnitz J M . Thermodynamics of mixed-gas adsorption [J ] . AIChE Journal , 1965 , 11 ( 1 ): 121 - 127 .

Kumar K V , Gadipelli S , Wood B , et al . Characterization of the adsorption site energies and heterogeneous surfaces of porous materials [J ] . Journal of Materials Chemistry A , 2019 , 7 ( 17 ): 10104 - 10137 .

Chen F Q , Ding J Q , Guo K Q , et al . CoNi alloy nanoparticles embedded in metal–organic framework-derived carbon for the highly efficient separation of xenon and krypton via a charge-transfer effect [J ] . Angewandte Chemie , 2021 , 133 ( 5 ): 2461 - 2468 .

Wang H , Yao K X , Zhang Z J , et al . The first example of commensurate adsorption of atomic gas in a MOF and effective separation of xenon from other noble gases [J ] . Chem Sci , 2014 , 5 ( 2 ): 620 - 624 .

Liu P X , Li J H , Yan F R , et al . A metal-organic framework with tailored shape-matched interactions towards ambient-temperature argon removal for oxygen purification [J ] . Angewandte Chemie , 2025 , 137 ( 25 ): e202504324 .

Yang Y N , Wang Y T , Zhang F F , et al . Synergistic weak hydrogen bonding interactions of methane in a green and scalable biological metal-organic framework for efficient CH 4 /N 2 separation [J ] . Chemical Engineering Journal , 2026 , 535 : 175426 .

Wang Y T , Zhang F F , Yang Y N , et al . Optimizing the pore environment in biological metal–organic frameworks through the incorporation of hydrogen bond acceptors for inverse ethane/ethylene separation [J ] . Journal of Colloid and Interface Science , 2025 , 687 : 439 - 448 .

Zhang L , Wang Y , Chen Y , et al . Metal-organic frameworks for ethane-selective adsorption: a comprehensive review on structural design and separation applications [J ] . Coordination Chemistry Reviews , 2025 , 544 : 216974 .

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