An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2

Maw Lin Foo; Ryotaro Matsuda; Yuh Hijikata; Rajamani Krishna; Hiroshi Sato; Satoshi Horike; Akihiro Hori; Jingui Duan; Yohei Sato; Yoshiki Kubota; Masaki Takata; Susumu Kitagawa

doi:10.1021/jacs.5b10491

An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO₂ over C₂H₂

Maw Lin Foo, Ryotaro Matsuda, Yuh Hijikata, Rajamani Krishna, Hiroshi Sato, Satoshi Horike, Akihiro Hori, Jingui Duan, Yohei Sato, Yoshiki Kubota, Masaki Takata, Susumu Kitagawa

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366 Scopus citations

Abstract

The adsorptive separation of C₂H₂ and CO₂ via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H₂bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C₂H₂ but not for CO₂, leading to an appreciable selective adsorption of CO₂ over C₂H₂ at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO₂/C₂H₂ selectivity, verifying the mechanism of the guest discriminatory gate effect.

Original language	English
Pages (from-to)	3022-3030
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	138
Issue number	9
DOIs	https://doi.org/10.1021/jacs.5b10491
State	Published - 9 Mar 2016
Externally published	Yes

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Foo, M. L., Matsuda, R., Hijikata, Y., Krishna, R., Sato, H., Horike, S., Hori, A., Duan, J., Sato, Y., Kubota, Y., Takata, M., & Kitagawa, S. (2016). An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO₂ over C₂H₂ Journal of the American Chemical Society, 138(9), 3022-3030. https://doi.org/10.1021/jacs.5b10491

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title = "An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2 ",

abstract = "The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect.",

author = "Foo, {Maw Lin} and Ryotaro Matsuda and Yuh Hijikata and Rajamani Krishna and Hiroshi Sato and Satoshi Horike and Akihiro Hori and Jingui Duan and Yohei Sato and Yoshiki Kubota and Masaki Takata and Susumu Kitagawa",

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Foo, ML, Matsuda, R, Hijikata, Y, Krishna, R, Sato, H, Horike, S, Hori, A, Duan, J, Sato, Y, Kubota, Y, Takata, M & Kitagawa, S 2016, 'An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO₂ over C₂H₂ ', Journal of the American Chemical Society, vol. 138, no. 9, pp. 3022-3030. https://doi.org/10.1021/jacs.5b10491

TY - JOUR

T1 - An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2

AU - Foo, Maw Lin

AU - Matsuda, Ryotaro

AU - Hijikata, Yuh

AU - Krishna, Rajamani

AU - Sato, Hiroshi

AU - Horike, Satoshi

AU - Hori, Akihiro

AU - Duan, Jingui

AU - Sato, Yohei

AU - Kubota, Yoshiki

AU - Takata, Masaki

AU - Kitagawa, Susumu

PY - 2016/3/9

Y1 - 2016/3/9

N2 - The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect.

AB - The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect.

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An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO₂ over C₂H₂

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