A Robust Molecular Porous Material for C2H2/CO2 Separation

Mei Yan Gao; Debobroto Sensharma; Andrey A. Bezrukov; Yassin H. Andaloussi; Shaza Darwish; Chenghua Deng; Matthias Vandichel; Jian Zhang; Michael J. Zaworotko

doi:10.1002/smll.202206945

A Robust Molecular Porous Material for C₂H₂/CO₂ Separation

Mei Yan Gao, Debobroto Sensharma, Andrey A. Bezrukov, Yassin H. Andaloussi, Shaza Darwish, Chenghua Deng, Matthias Vandichel, Jian Zhang, Michael J. Zaworotko

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

Abstract

A molecular porous material, MPM-2, comprised of cationic [Ni₂(AlF₆)(pzH)₈(H₂O)₂] and anionic [Ni₂Al₂F₁₁(pzH)₈(H₂O)₂] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C₂H₂ over CO₂ thanks to a high (ΔQ_st)_AC [Q_st (C₂H₂) − Q_st (CO₂)] of 13.7 kJ mol⁻¹ at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C₂H₂ from a 1:1 C₂H₂/CO₂ mixture at 298 K with effluent CO₂ purity of 99.995% and C₂H₂ purity of >95% after temperature-programmed desorption. C-H···F interactions between C₂H₂ molecules and F atoms of AlF₆³⁻ are found to enable high selectivity toward C₂H₂, as determined by density functional theory simulations.

Original language	English
Article number	2206945
Journal	Small
Volume	19
Issue number	11
DOIs	https://doi.org/10.1002/smll.202206945
Publication status	Published - 15 Mar 2023

Keywords

C H /CO separation
hydrogen bonds
molecular porous materials
pcu topology
purification

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10.1002/smll.202206945

Cite this

@article{09bc4187ab264e16b034a10b48419ed6,

title = "A Robust Molecular Porous Material for C2H2/CO2 Separation",

abstract = "A molecular porous material, MPM-2, comprised of cationic [Ni2(AlF6)(pzH)8(H2O)2] and anionic [Ni2Al2F11(pzH)8(H2O)2] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2H2 over CO2 thanks to a high (ΔQst)AC [Qst (C2H2) − Qst (CO2)] of 13.7 kJ mol−1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2H2 from a 1:1 C2H2/CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2H2 molecules and F atoms of AlF63− are found to enable high selectivity toward C2H2, as determined by density functional theory simulations.",

keywords = "C H /CO separation, hydrogen bonds, molecular porous materials, pcu topology, purification",

author = "Gao, {Mei Yan} and Debobroto Sensharma and Bezrukov, {Andrey A.} and Andaloussi, {Yassin H.} and Shaza Darwish and Chenghua Deng and Matthias Vandichel and Jian Zhang and Zaworotko, {Michael J.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Small published by Wiley-VCH GmbH.",

year = "2023",

month = mar,

day = "15",

doi = "10.1002/smll.202206945",

language = "English",

volume = "19",

journal = "Small",

issn = "1613-6810",

number = "11",

}

TY - JOUR

T1 - A Robust Molecular Porous Material for C2H2/CO2 Separation

AU - Gao, Mei Yan

AU - Sensharma, Debobroto

AU - Bezrukov, Andrey A.

AU - Andaloussi, Yassin H.

AU - Darwish, Shaza

AU - Deng, Chenghua

AU - Vandichel, Matthias

AU - Zhang, Jian

AU - Zaworotko, Michael J.

PY - 2023/3/15

Y1 - 2023/3/15

N2 - A molecular porous material, MPM-2, comprised of cationic [Ni2(AlF6)(pzH)8(H2O)2] and anionic [Ni2Al2F11(pzH)8(H2O)2] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2H2 over CO2 thanks to a high (ΔQst)AC [Qst (C2H2) − Qst (CO2)] of 13.7 kJ mol−1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2H2 from a 1:1 C2H2/CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2H2 molecules and F atoms of AlF63− are found to enable high selectivity toward C2H2, as determined by density functional theory simulations.

AB - A molecular porous material, MPM-2, comprised of cationic [Ni2(AlF6)(pzH)8(H2O)2] and anionic [Ni2Al2F11(pzH)8(H2O)2] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2H2 over CO2 thanks to a high (ΔQst)AC [Qst (C2H2) − Qst (CO2)] of 13.7 kJ mol−1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2H2 from a 1:1 C2H2/CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2H2 molecules and F atoms of AlF63− are found to enable high selectivity toward C2H2, as determined by density functional theory simulations.

KW - C H /CO separation

KW - hydrogen bonds

KW - molecular porous materials

KW - pcu topology

KW - purification

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U2 - 10.1002/smll.202206945

DO - 10.1002/smll.202206945

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VL - 19

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M1 - 2206945

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