Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation

Yuanmeng Tian; Zeyu Tao; Changwei Liu; Mingzhe Sun; Chungkai Chang; Qinfen Gu; Liangchun Li; Jin Shang

doi:10.1016/j.cej.2024.150293

Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation

Yuanmeng Tian (Co-first Author), Zeyu Tao (Co-first Author), Changwei Liu, Mingzhe Sun, Chungkai Chang, Qinfen Gu^*, Liangchun Li^*, Jin Shang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

2 Citations (Scopus)

Abstract

Exclusive admission of targeted gas molecules by porous materials, i.e., molecular sieving, is highly sought-after to afford highly selective separation but is challenging when gas molecules have similar sizes. Although the “molecular trapdoor” mechanism discovered in zeolites allows for addressing this challenge, the limited adaptability of zeolites constrains the full harnessing of this mechanism. In this study, we have identified a cage-type of stimuli-responsive metal–organic framework (MOF) as a “molecular trapdoor” material through a combined experimental and simulation approach by adjusting its gate-opening behavior via anion modulation. The temperature-dependent gas admission observed does not merely result from the thermal motion of “gate-keeping” anions, but rather emerges from their interaction with guest molecules within the pore. By modifying the “gate-keeping” groups, we achieved the highest selectivity of CO₂/N₂ (697) and CO₂/CH₄ (22) at 273 K in ClO₄-BTR MOF in this study. Additionally, we have identified a consistent pattern governing the diffusion rate during the gas adsorption process among NO₃-BTR, BF₄-BTR, and ClO₄-BTR MOFs concerning variations in temperature and pressure. This work unveils the fundamental mechanism and enhances our understanding of gas admission in a MOF featuring pore-blocking anions, thus expanding the prospective applications of MOFs as “molecular trapdoor” adsorbents and offering valuable guidance for the strategic design of ionic MOFs with specific gas separation characteristics.

© 2024 Elsevier B.V.

Original language	English
Article number	150293
Number of pages	9
Journal	Chemical Engineering Journal
Volume	486
Online published	11 Mar 2024
DOIs	https://doi.org/10.1016/j.cej.2024.150293
Publication status	Published - 15 Apr 2024

Funding

This work was financially supported by the Science and Technology Innovation Commission of Shenzhen Municipality (Ref: JCYJ20210324134006019), the Research Grants Council of Hong Kong (Ref: CityU 11317722 , 11310223 ), and the National Natural Science Foundation of China (No. 22371210 ). This research was undertaken in part using the MX2 beamlines at the Australian Synchrotron, part of ANSTO, and made use of the Australian Cancer Research Foundation (ACRF) detector. The authors express their gratitude to the beamline TPS-19A at National Synchrotron Radiation Research Center (NSRRC) in Taiwan. The technical assistance from Ms. Shanshan Shang is appreciated.

Research Keywords

Exclusive admission
Gate-keeping groups
Molecular trapdoor

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COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: © 2024 Elsevier B.V. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/.

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abstract = "Exclusive admission of targeted gas molecules by porous materials, i.e., molecular sieving, is highly sought-after to afford highly selective separation but is challenging when gas molecules have similar sizes. Although the “molecular trapdoor” mechanism discovered in zeolites allows for addressing this challenge, the limited adaptability of zeolites constrains the full harnessing of this mechanism. In this study, we have identified a cage-type of stimuli-responsive metal–organic framework (MOF) as a “molecular trapdoor” material through a combined experimental and simulation approach by adjusting its gate-opening behavior via anion modulation. The temperature-dependent gas admission observed does not merely result from the thermal motion of “gate-keeping” anions, but rather emerges from their interaction with guest molecules within the pore. By modifying the “gate-keeping” groups, we achieved the highest selectivity of CO2/N2 (697) and CO2/CH4 (22) at 273 K in ClO4-BTR MOF in this study. Additionally, we have identified a consistent pattern governing the diffusion rate during the gas adsorption process among NO3-BTR, BF4-BTR, and ClO4-BTR MOFs concerning variations in temperature and pressure. This work unveils the fundamental mechanism and enhances our understanding of gas admission in a MOF featuring pore-blocking anions, thus expanding the prospective applications of MOFs as “molecular trapdoor” adsorbents and offering valuable guidance for the strategic design of ionic MOFs with specific gas separation characteristics. {\textcopyright} 2024 Elsevier B.V.",

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Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation. / Tian, Yuanmeng (Co-first Author); Tao, Zeyu (Co-first Author); Liu, Changwei et al.
In: Chemical Engineering Journal, Vol. 486, 150293, 15.04.2024.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation

AU - Tian, Yuanmeng

AU - Tao, Zeyu

AU - Liu, Changwei

AU - Sun, Mingzhe

AU - Chang, Chungkai

AU - Gu, Qinfen

AU - Li, Liangchun

AU - Shang, Jin

PY - 2024/4/15

Y1 - 2024/4/15

N2 - Exclusive admission of targeted gas molecules by porous materials, i.e., molecular sieving, is highly sought-after to afford highly selective separation but is challenging when gas molecules have similar sizes. Although the “molecular trapdoor” mechanism discovered in zeolites allows for addressing this challenge, the limited adaptability of zeolites constrains the full harnessing of this mechanism. In this study, we have identified a cage-type of stimuli-responsive metal–organic framework (MOF) as a “molecular trapdoor” material through a combined experimental and simulation approach by adjusting its gate-opening behavior via anion modulation. The temperature-dependent gas admission observed does not merely result from the thermal motion of “gate-keeping” anions, but rather emerges from their interaction with guest molecules within the pore. By modifying the “gate-keeping” groups, we achieved the highest selectivity of CO2/N2 (697) and CO2/CH4 (22) at 273 K in ClO4-BTR MOF in this study. Additionally, we have identified a consistent pattern governing the diffusion rate during the gas adsorption process among NO3-BTR, BF4-BTR, and ClO4-BTR MOFs concerning variations in temperature and pressure. This work unveils the fundamental mechanism and enhances our understanding of gas admission in a MOF featuring pore-blocking anions, thus expanding the prospective applications of MOFs as “molecular trapdoor” adsorbents and offering valuable guidance for the strategic design of ionic MOFs with specific gas separation characteristics. © 2024 Elsevier B.V.

AB - Exclusive admission of targeted gas molecules by porous materials, i.e., molecular sieving, is highly sought-after to afford highly selective separation but is challenging when gas molecules have similar sizes. Although the “molecular trapdoor” mechanism discovered in zeolites allows for addressing this challenge, the limited adaptability of zeolites constrains the full harnessing of this mechanism. In this study, we have identified a cage-type of stimuli-responsive metal–organic framework (MOF) as a “molecular trapdoor” material through a combined experimental and simulation approach by adjusting its gate-opening behavior via anion modulation. The temperature-dependent gas admission observed does not merely result from the thermal motion of “gate-keeping” anions, but rather emerges from their interaction with guest molecules within the pore. By modifying the “gate-keeping” groups, we achieved the highest selectivity of CO2/N2 (697) and CO2/CH4 (22) at 273 K in ClO4-BTR MOF in this study. Additionally, we have identified a consistent pattern governing the diffusion rate during the gas adsorption process among NO3-BTR, BF4-BTR, and ClO4-BTR MOFs concerning variations in temperature and pressure. This work unveils the fundamental mechanism and enhances our understanding of gas admission in a MOF featuring pore-blocking anions, thus expanding the prospective applications of MOFs as “molecular trapdoor” adsorbents and offering valuable guidance for the strategic design of ionic MOFs with specific gas separation characteristics. © 2024 Elsevier B.V.

KW - Exclusive admission

KW - Gate-keeping groups

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DO - 10.1016/j.cej.2024.150293

M3 - RGC 21 - Publication in refereed journal

SN - 1385-8947

VL - 486

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

M1 - 150293

ER -

Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation

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GRF: Selective Gas Adsorption by Single-atom Extraframework Transition Metal Sites Regularly Arranged Inside Porous Crystalline Matrices

GRF: Develop Robust Metal-Organic Frameworks-based Adsorbents for Toxic and Corrosive Gases: Importance of Specific Binding Sites and Adsorption-Desorption Mechanism

Cite this

Adjusting gate-opening behavior in a rigid cage-type “molecular trapdoor” metal–organic framework via anion modulation

Abstract

Funding

Research Keywords

Publisher's Copyright Statement

RGC Funding Information

Access Output

Other Access Options

Permanent Link

Other Files and Links

Embargoed Document

Fingerprint

Projects

GRF: Selective Gas Adsorption by Single-atom Extraframework Transition Metal Sites Regularly Arranged Inside Porous Crystalline Matrices

GRF: Develop Robust Metal-Organic Frameworks-based Adsorbents for Toxic and Corrosive Gases: Importance of Specific Binding Sites and Adsorption-Desorption Mechanism

Cite this