Facile loading of Cu(I) in MIL-100(Fe) through redox-active Fe(II) sites and remarkable propylene/propane separation performance

Ah Reum Kim; Tae Ung Yoon; Eun Jung Kim; Jung Woon Yoon; Seo Yul Kim; Ji Woong Yoon; Young Kyu Hwang; Jong San Chang; Youn Sang Bae

doi:10.1016/j.cej.2017.09.016

Facile loading of Cu(I) in MIL-100(Fe) through redox-active Fe(II) sites and remarkable propylene/propane separation performance

Ah Reum Kim, Tae Ung Yoon, Eun Jung Kim, Jung Woon Yoon, Seo Yul Kim, Ji Woong Yoon, Young Kyu Hwang, Jong San Chang, Youn Sang Bae

Department of Chemical and Biomolecular Engineering

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

70 Citations (Scopus)

Abstract

A novel Cu(I) loading method, which includes the reduction of CuCl₂ to CuCl without an external reducing agent and high-temperature calcination, was developed using the redox properties of coordinatively unsaturated Fe(II) sites in MIL-100(Fe). The successful loading of Cu(I) ions and their redox-couple reactions are supported by various methods such as TEM/EDS, XPS, PXRD, and ICP-AES techniques, as well as N₂ adsorption isotherms at 77 K. Compared to Cu loaded into isostructural MIL-100(Al) devoid of redox active sites, Cu(I)-loaded MIL-100(Fe) exhibits higher C₃H₆/C₃H₈ selectivity and superior air stability. This indicates that the Fe(II) sites in MIL-100(Fe) act as antioxidants that protect the resultant Cu(I) species, as well as reducing agents for CuCl₂. Remarkably, in the typical pressure-swing adsorption (PSA) range (1–5 bar), the Cu(I)-loaded MIL-100(Fe) exhibits a large C₃H₆ working capacity as well as very high C₃H₆/C₃H₈ selectivities that are superior to those of the benchmark adsorbents, zeolite-13X and HKUST-1. Moreover, this material is easily regenerated under mild conditions and exhibits good separation performance under dynamic mixed-flow conditions. This facile method for loading Cu(I) can be applied to other adsorbents containing redox-active sites.

Original language	English
Pages (from-to)	777-784
Number of pages	8
Journal	Chemical Engineering Journal
Volume	331
DOIs	https://doi.org/10.1016/j.cej.2017.09.016
Publication status	Published - 2018 Jan 1

Bibliographical note

Funding Information:
We would like to acknowledge the National Research Council of Science & Technology (NST) grant by the Korea government (MSIP) (No. CRC-14-1-KRICT ). This work was also supported by In-house Research and Development Program of the Korea Institute of Energy Research (KIER) ( B7-2437-03 ).

Publisher Copyright:
© 2017 Elsevier B.V.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Environmental Chemistry
Chemical Engineering(all)
Industrial and Manufacturing Engineering

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10.1016/j.cej.2017.09.016

Cite this

@article{ca8a2535d5e544edb8fc55d9e778f6c6,

title = "Facile loading of Cu(I) in MIL-100(Fe) through redox-active Fe(II) sites and remarkable propylene/propane separation performance",

abstract = "A novel Cu(I) loading method, which includes the reduction of CuCl2 to CuCl without an external reducing agent and high-temperature calcination, was developed using the redox properties of coordinatively unsaturated Fe(II) sites in MIL-100(Fe). The successful loading of Cu(I) ions and their redox-couple reactions are supported by various methods such as TEM/EDS, XPS, PXRD, and ICP-AES techniques, as well as N2 adsorption isotherms at 77 K. Compared to Cu loaded into isostructural MIL-100(Al) devoid of redox active sites, Cu(I)-loaded MIL-100(Fe) exhibits higher C3H6/C3H8 selectivity and superior air stability. This indicates that the Fe(II) sites in MIL-100(Fe) act as antioxidants that protect the resultant Cu(I) species, as well as reducing agents for CuCl2. Remarkably, in the typical pressure-swing adsorption (PSA) range (1–5 bar), the Cu(I)-loaded MIL-100(Fe) exhibits a large C3H6 working capacity as well as very high C3H6/C3H8 selectivities that are superior to those of the benchmark adsorbents, zeolite-13X and HKUST-1. Moreover, this material is easily regenerated under mild conditions and exhibits good separation performance under dynamic mixed-flow conditions. This facile method for loading Cu(I) can be applied to other adsorbents containing redox-active sites.",

author = "Kim, {Ah Reum} and Yoon, {Tae Ung} and Kim, {Eun Jung} and Yoon, {Jung Woon} and Kim, {Seo Yul} and Yoon, {Ji Woong} and Hwang, {Young Kyu} and Chang, {Jong San} and Bae, {Youn Sang}",

note = "Funding Information: We would like to acknowledge the National Research Council of Science & Technology (NST) grant by the Korea government (MSIP) (No. CRC-14-1-KRICT ). This work was also supported by In-house Research and Development Program of the Korea Institute of Energy Research (KIER) ( B7-2437-03 ). Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2018",

month = jan,

day = "1",

doi = "10.1016/j.cej.2017.09.016",

language = "English",

volume = "331",

pages = "777--784",

journal = "Chemical Engineering Journal",

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T1 - Facile loading of Cu(I) in MIL-100(Fe) through redox-active Fe(II) sites and remarkable propylene/propane separation performance

AU - Kim, Ah Reum

AU - Yoon, Tae Ung

AU - Kim, Eun Jung

AU - Yoon, Jung Woon

AU - Kim, Seo Yul

AU - Yoon, Ji Woong

AU - Hwang, Young Kyu

AU - Chang, Jong San

AU - Bae, Youn Sang

N1 - Funding Information: We would like to acknowledge the National Research Council of Science & Technology (NST) grant by the Korea government (MSIP) (No. CRC-14-1-KRICT ). This work was also supported by In-house Research and Development Program of the Korea Institute of Energy Research (KIER) ( B7-2437-03 ). Publisher Copyright: © 2017 Elsevier B.V.

PY - 2018/1/1

Y1 - 2018/1/1

N2 - A novel Cu(I) loading method, which includes the reduction of CuCl2 to CuCl without an external reducing agent and high-temperature calcination, was developed using the redox properties of coordinatively unsaturated Fe(II) sites in MIL-100(Fe). The successful loading of Cu(I) ions and their redox-couple reactions are supported by various methods such as TEM/EDS, XPS, PXRD, and ICP-AES techniques, as well as N2 adsorption isotherms at 77 K. Compared to Cu loaded into isostructural MIL-100(Al) devoid of redox active sites, Cu(I)-loaded MIL-100(Fe) exhibits higher C3H6/C3H8 selectivity and superior air stability. This indicates that the Fe(II) sites in MIL-100(Fe) act as antioxidants that protect the resultant Cu(I) species, as well as reducing agents for CuCl2. Remarkably, in the typical pressure-swing adsorption (PSA) range (1–5 bar), the Cu(I)-loaded MIL-100(Fe) exhibits a large C3H6 working capacity as well as very high C3H6/C3H8 selectivities that are superior to those of the benchmark adsorbents, zeolite-13X and HKUST-1. Moreover, this material is easily regenerated under mild conditions and exhibits good separation performance under dynamic mixed-flow conditions. This facile method for loading Cu(I) can be applied to other adsorbents containing redox-active sites.

AB - A novel Cu(I) loading method, which includes the reduction of CuCl2 to CuCl without an external reducing agent and high-temperature calcination, was developed using the redox properties of coordinatively unsaturated Fe(II) sites in MIL-100(Fe). The successful loading of Cu(I) ions and their redox-couple reactions are supported by various methods such as TEM/EDS, XPS, PXRD, and ICP-AES techniques, as well as N2 adsorption isotherms at 77 K. Compared to Cu loaded into isostructural MIL-100(Al) devoid of redox active sites, Cu(I)-loaded MIL-100(Fe) exhibits higher C3H6/C3H8 selectivity and superior air stability. This indicates that the Fe(II) sites in MIL-100(Fe) act as antioxidants that protect the resultant Cu(I) species, as well as reducing agents for CuCl2. Remarkably, in the typical pressure-swing adsorption (PSA) range (1–5 bar), the Cu(I)-loaded MIL-100(Fe) exhibits a large C3H6 working capacity as well as very high C3H6/C3H8 selectivities that are superior to those of the benchmark adsorbents, zeolite-13X and HKUST-1. Moreover, this material is easily regenerated under mild conditions and exhibits good separation performance under dynamic mixed-flow conditions. This facile method for loading Cu(I) can be applied to other adsorbents containing redox-active sites.

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DO - 10.1016/j.cej.2017.09.016

M3 - Article

AN - SCOPUS:85033668268

SN - 1385-8947

VL - 331

SP - 777

EP - 784

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

ER -

Facile loading of Cu(I) in MIL-100(Fe) through redox-active Fe(II) sites and remarkable propylene/propane separation performance

Abstract

Bibliographical note

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