Unexpected Penetration of CO Molecule into Zeolitic Micropores Almost Plugged by CuCl via π-Complexation of CO-CuCl

Chan Hyun Lee, Kwangsoo Kim, Jisoo Kim, Kanghee Cho, Sang Sup Han, Hyun Wook Kim, Ki Bong Lee, Byung Hyun Kim, Jong Hyeok Park, Kyoungsoo Kim, Jong Ho Park

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)


Carbon monoxide (CO) is a key reactant in several Fischer-Tropsch processes, including those used in light olefin and methanol syntheses. However, it is highly toxic and causes serious poisoning of noble metal catalysts. Thus, a solid adsorbent that can selectively capture CO, especially at low concentrations, is required. In this study, zeolite Y-based adsorbents in which Cu(I) ions occupy the supercage cation sites (CuCl/Y) are prepared via solid-state ion exchange. Volumetric adsorption measurements reveal that the Cu(I) ions significantly enhance CO adsorption in the low-pressure range by π-complexation. Furthermore, unexpected molecular sieving behavior, with extremely high CO/CO2 selectivity, is observed when excess CuCl homogeneously covers the zeolite pore structures. Thus, although CO has a larger kinetic diameter, it can penetrate the zeolite supercage while smaller molecules (i.e., Ar and CO2) cannot. Density functional theory calculations reveal that CO molecules can remain adsorbed in pseudoblocked pores by CuCl, thanks to the strong interaction of C 2p and Cu 3d states, resulting in the high CO/CO2 selectivity. One of the prepared adsorbents, CuCl/Y with 50 wt % CuCl, is capable of selectively capturing 3.04 mmol g-1 of CO with a CO/CO2 selectivity of >3370.

Original languageEnglish
Pages (from-to)27411-27421
Number of pages11
JournalACS Applied Materials and Interfaces
Issue number22
Publication statusPublished - 2023 Jun 7

Bibliographical note

Funding Information:
This work was conducted under the framework of the research and development program of National Research Foundation of Korea (NRF), funded by the Korean Government Ministry of Science and ICT (2022M3J2A1085669). C.H.L. acknowledges additional financial support by Regional Innovation Strategy (RIS) through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2021RIS-003).

Publisher Copyright:
© 2023 American Chemical Society.


  • Molecular sieving
  • adsorbent
  • density functional theory
  • kinetic diameter
  • π-complexation

ASJC Scopus subject areas

  • General Materials Science


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