Exploring the Fluorination and Hydroxylation of Pore-Space-Partitioned Metal−Organic Frameworks for C2H2/CH4 Separation

Rajeshkumar Anbazhagan; Tai Sheng Wang; Hao Ping Kuan; Ilja Popovs; Hsin Kuan Liu; Tsu Lien Hung; Watchareeya Kaveevivitchai; Teng Hao Chen

doi:10.1002/asia.202401329

Exploring the Fluorination and Hydroxylation of Pore-Space-Partitioned Metal−Organic Frameworks for C₂H₂/CH₄ Separation

Rajeshkumar Anbazhagan, Tai Sheng Wang, Hao Ping Kuan, Ilja Popovs, Hsin Kuan Liu, Tsu Lien Hung, Watchareeya Kaveevivitchai, Teng Hao Chen

Nanomaterials Chemistry Group

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

We report three novel pore-space-partitioned metal−organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F₄-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F₂(OH)₂-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F₄ (NCKU-21), Mn-TPT-BDC-F₂(OH)₂ (NCKU-22), and Mg-TPT-BDC-F₂(OH)₂ (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors. Although NCKU-22 uptakes a much lower amount of C₂H₂ compared to NCKU-21 and -23, dynamic breakthrough experiments show that these three materials are all capable of efficient C₂H₂/CH₄ separations. These MOFs possess moderate isosteric heat of adsorption for C₂H₂ (25.7–32.1 kJ mol⁻¹), allowing easy regeneration and energy-efficient C₂H₂/CH₄ separations.

Original language	English
Article number	e202401329
Journal	Chemistry - An Asian Journal
Volume	20
Issue number	6
DOIs	https://doi.org/10.1002/asia.202401329
State	Published - Mar 17 2025

Funding

This work was supported by the National Science and Technology Council (NSTC) of Taiwan under grants NSTC 112–2113-M-006–004 (to T.-H. C.), NSTC 111–2221-E-006–011-MY3, and 112–2221-E-006–021-MY3 (to W. K.). This work was also financially supported by the Hierarchical Green-Energy Materials (Hi-GEM) Research Center from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) in Taiwan (to W. K.). This research was supported in part by High Education Sprout Project, MOE of the Headquarters of University Advancement at NCKU (to T.-H. C. and W. K.). The work by I. P. was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Separation Science program, and Materials Chemistry program under award no. DE-SC00ERKCG21. The authors gratefully acknowledge the use of EA000600, NMR005000, MS0000003300, NMR001900, and XRD003100 of NSTC 112–2740-M-006–001 belonging to the Core Facility Center of NCKU. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05–00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript or allow others to do so for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan). This work was supported by the National Science and Technology Council (NSTC) of Taiwan under grants NSTC 112–2113‐M‐006–004 (to T.‐H. C.), NSTC 111–2221‐E‐006–011‐MY3, and 112–2221‐E‐006–021‐MY3 (to W. K.). This work was also financially supported by the Hierarchical Green‐Energy Materials (Hi‐GEM) Research Center from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) in Taiwan (to W. K.). This research was supported in part by High Education Sprout Project, MOE of the Headquarters of University Advancement at NCKU (to T.‐H. C. and W. K.). The work by I. P. was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Separation Science program, and Materials Chemistry program under award no. DE‐SC00ERKCG21. The authors gratefully acknowledge the use of EA000600, NMR005000, MS0000003300, NMR001900, and XRD003100 of NSTC 112–2740‐M‐006–001 belonging to the Core Facility Center of NCKU. This manuscript has been authored in part by UT‐Battelle, LLC, under contract DE‐AC05–00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript or allow others to do so for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( https://energy.gov/downloads/doe‐public‐access‐plan ).

Keywords

Acetylene separation
Fluorination
Hydroxylation
Metal−organic frameworks
Pore space partition

Access to Document

10.1002/asia.202401329

Cite this

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title = "Exploring the Fluorination and Hydroxylation of Pore-Space-Partitioned Metal−Organic Frameworks for C2H2/CH4 Separation",

abstract = "We report three novel pore-space-partitioned metal−organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F4-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F2(OH)2-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F4 (NCKU-21), Mn-TPT-BDC-F2(OH)2 (NCKU-22), and Mg-TPT-BDC-F2(OH)2 (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors. Although NCKU-22 uptakes a much lower amount of C2H2 compared to NCKU-21 and -23, dynamic breakthrough experiments show that these three materials are all capable of efficient C2H2/CH4 separations. These MOFs possess moderate isosteric heat of adsorption for C2H2 (25.7–32.1 kJ mol−1), allowing easy regeneration and energy-efficient C2H2/CH4 separations.",

keywords = "Acetylene separation, Fluorination, Hydroxylation, Metal−organic frameworks, Pore space partition",

author = "Rajeshkumar Anbazhagan and Wang, \{Tai Sheng\} and Kuan, \{Hao Ping\} and Ilja Popovs and Liu, \{Hsin Kuan\} and Hung, \{Tsu Lien\} and Watchareeya Kaveevivitchai and Chen, \{Teng Hao\}",

note = "Publisher Copyright: {\textcopyright} 2025 Wiley-VCH GmbH.",

year = "2025",

month = mar,

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doi = "10.1002/asia.202401329",

language = "English",

volume = "20",

journal = "Chemistry - An Asian Journal",

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T1 - Exploring the Fluorination and Hydroxylation of Pore-Space-Partitioned Metal−Organic Frameworks for C2H2/CH4 Separation

AU - Anbazhagan, Rajeshkumar

AU - Wang, Tai Sheng

AU - Kuan, Hao Ping

AU - Popovs, Ilja

AU - Liu, Hsin Kuan

AU - Hung, Tsu Lien

AU - Kaveevivitchai, Watchareeya

AU - Chen, Teng Hao

PY - 2025/3/17

Y1 - 2025/3/17

N2 - We report three novel pore-space-partitioned metal−organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F4-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F2(OH)2-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F4 (NCKU-21), Mn-TPT-BDC-F2(OH)2 (NCKU-22), and Mg-TPT-BDC-F2(OH)2 (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors. Although NCKU-22 uptakes a much lower amount of C2H2 compared to NCKU-21 and -23, dynamic breakthrough experiments show that these three materials are all capable of efficient C2H2/CH4 separations. These MOFs possess moderate isosteric heat of adsorption for C2H2 (25.7–32.1 kJ mol−1), allowing easy regeneration and energy-efficient C2H2/CH4 separations.

AB - We report three novel pore-space-partitioned metal−organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F4-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F2(OH)2-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F4 (NCKU-21), Mn-TPT-BDC-F2(OH)2 (NCKU-22), and Mg-TPT-BDC-F2(OH)2 (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors. Although NCKU-22 uptakes a much lower amount of C2H2 compared to NCKU-21 and -23, dynamic breakthrough experiments show that these three materials are all capable of efficient C2H2/CH4 separations. These MOFs possess moderate isosteric heat of adsorption for C2H2 (25.7–32.1 kJ mol−1), allowing easy regeneration and energy-efficient C2H2/CH4 separations.

KW - Acetylene separation

KW - Fluorination

KW - Hydroxylation

KW - Metal−organic frameworks

KW - Pore space partition

UR - https://www.scopus.com/pages/publications/105001064833

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DO - 10.1002/asia.202401329

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AN - SCOPUS:105001064833

SN - 1861-4728

VL - 20

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

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ER -