Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles

Donglin He; Linda Zhang; Tao Liu; Rob Clowes; Marc A. Little; Ming Liu; Michael Hirscher; Andrew I. Cooper

doi:10.1002/anie.202202450

Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles

Donglin He, Linda Zhang^*, Tao Liu, Rob Clowes, Marc A. Little^*, Ming Liu^*, Michael Hirscher, Andrew I. Cooper^*

^*Corresponding author for this work

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

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Abstract

Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and Zn II ions that exhibits narrow windows (<3.0 Å). Two polymorphs, referred to as 2α and 2β, were observed. Both polymorphs exhibit D₂ /H₂ selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D₂ adsorption capacity of 2β increases to about 2.7 times that of 2α, along with a reasonable D₂ /H₂ selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments.

Original language	English
Article number	e202202450
Journal	Angewandte Chemie International Edition
Volume	61
Issue number	32
Early online date	10 Jun 2022
DOIs	https://doi.org/10.1002/anie.202202450
Publication status	Published - 8 Aug 2022

Keywords

porous material
quantum sieving
gas separation
metal organic cages
X-ray crystallography
crystal engineering
organic macrocycles

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title = "Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles",

abstract = "Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and Zn II ions that exhibits narrow windows (<3.0 {\AA}). Two polymorphs, referred to as 2α and 2β, were observed. Both polymorphs exhibit D2 /H2 selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D2 adsorption capacity of 2β increases to about 2.7 times that of 2α, along with a reasonable D2 /H2 selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments. ",

keywords = "porous material, quantum sieving, gas separation, metal organic cages, X-ray crystallography, crystal engineering, organic macrocycles",

author = "Donglin He and Linda Zhang and Tao Liu and Rob Clowes and Little, {Marc A.} and Ming Liu and Michael Hirscher and Cooper, {Andrew I.}",

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AU - He, Donglin

AU - Zhang, Linda

AU - Liu, Tao

AU - Clowes, Rob

AU - Little, Marc A.

AU - Liu, Ming

AU - Hirscher, Michael

AU - Cooper, Andrew I.

PY - 2022/8/8

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N2 - Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and Zn II ions that exhibits narrow windows (<3.0 Å). Two polymorphs, referred to as 2α and 2β, were observed. Both polymorphs exhibit D2 /H2 selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D2 adsorption capacity of 2β increases to about 2.7 times that of 2α, along with a reasonable D2 /H2 selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments.

AB - Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and Zn II ions that exhibits narrow windows (<3.0 Å). Two polymorphs, referred to as 2α and 2β, were observed. Both polymorphs exhibit D2 /H2 selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D2 adsorption capacity of 2β increases to about 2.7 times that of 2α, along with a reasonable D2 /H2 selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments.

KW - porous material

KW - quantum sieving

KW - gas separation

KW - metal organic cages

KW - X-ray crystallography

KW - crystal engineering

KW - organic macrocycles

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DO - 10.1002/anie.202202450

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VL - 61

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

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M1 - e202202450

ER -

Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles

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Keywords

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