Thermochemical evidence for strong iodine chemisorption by ZIF-8

James T. Hughes, Dorina F. Sava, Tina M. Nenoff, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

127 Scopus citations

Abstract

For the first time, using aqueous solution calorimetry, we clearly identify the chemisorption of an unusually strong iodine charge-transfer (CT) complex within the cages of a metal-organic framework. Specifically, we studied the sorption of iodine gas in zeolitic imidazolate framework-8 (ZIF-8, Zn(2-methylimidazolate)2). Two iodine-loaded ZIF-8 samples were examined. The first, before thermal treatment, contained 0.17 I2/Zn on the surface and 0.59 I2/Zn inside the cage. The second sample was thermally treated, leaving only cage-confined iodine, 0.59 I2/Zn. The energetics of iodine confinement per I2 (relative to solid I 2) in ZIF-8 are ΔHads = -41.47 ± 2.03 kJ/(mol I2) within the cage and ΔHads = -18.06 ± 0.62 kJ/(mol I2) for surface-bound iodine. The cage-confined iodine exhibits a 3-fold increase in binding energy over CT complexes on various organic adsorbents, which show only moderate exothermic heats of binding, from -5 to -15 kJ/(mol I2). The ZIF-8 cage geometry allows each iodine atom to form two CT complexes between opposing 2-methylimidazolate linkers, creating the ideal binding site to maximize iodine retention.

Original languageEnglish (US)
Pages (from-to)16256-16259
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number44
DOIs
StatePublished - Nov 6 2013
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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