Synthetic Origin-Dependent catalytic activity of Metal-Organic Frameworks: Unprecedented demonstration with ZIF-8 s on CO2 cycloaddition reaction

Gihoon Lee, Minseong Lee, Yanghwan Jeong, Eunhee Jang, Hionsuck Baik, Ji Chul Jung, Jungkyu Choi

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

In this study, the catalytic activities of three types of zeolitic imidazolate framework-8 (ZIF-8) (two types were synthesized in aqueous and methanolic media, while the other was commercially available) with respect to CO2 cycloaddition to epichlorohydrin were evaluated. Surprisingly, only the ZIF-8 that was synthesized in an aqueous medium showed a marked catalytic performance, leading to the generation of the desired product, chloropropene carbonate. On the contrary, the other two types of ZIF-8 showed little to no catalytic activity. It is conjectured that the water molecules occluded inside the as-synthesized ZIF-8 triggered the dissociation of Zn-N bonds, resulting in a concomitant transformation to a new, dense phase. Accordingly, it is plausible that dissociated Zn or N species were formed during the reaction. In particular, we found that the dissociated N species arising from the dissociation of Zn-N bonds were pyrrolic and pyridinic, while the dissociated Zn species were bound to hydroxyl groups. Finally, complementary interpretation of CO2– and NH3-based temperature-programmed desorption and NH3-adsorbed Fourier transform infrared spectroscopy results revealed that the dissociated Zn species connected with hydroxyl groups, observed only in the ZIF-8 synthesized in an aqueous medium, served simultaneously as Lewis acids and bases and, thus, were crucial to the CO2 cycloaddition reaction.

Original languageEnglish
Article number134964
JournalChemical Engineering Journal
Volume435
DOIs
Publication statusPublished - 2022 May 1

Keywords

  • CO cycloaddition
  • CO utilization
  • Structural transformation
  • Zeolitic imidazolate framework-8

ASJC Scopus subject areas

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

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