title: Thermochemical evidence for strong iodine chemisorption by ZIF-8.
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 I2) 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.
authors.affiliation: Peter A. Rock Thermochemistry Laboratory, NEAT ORU, University of California, Davis , One Shields Avenue, Davis, California 95616, United States.
authors.forename: James T
authors.initials: JT
authors.lastname: Hughes
authors.forename: Dorina F
authors.initials: DF
authors.lastname: Sava
authors.forename: Tina M
authors.initials: TM
authors.lastname: Nenoff
authors.forename: Alexandra
authors.initials: A
authors.lastname: Navrotsky