NDLI: Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M<sub>2</sub>(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)

Content Provider	Royal Society of Chemistry (RSC)
Author	Lee, Jason S. Lee, Kyuho Gonzalez, Miguel I. Neaton, Jeffrey B. Queen, Wendy L. Brown, Craig M. Peterson, Vanessa K. Hudson, Matthew R. Gygi, David Long, Jeffrey R. Teat, Simon J. Bloch, Eric D. Darwish, Tamim A. James, Michael Mason, Jarad A. Howe, Joshua D. Smit, Berend
Copyright Year	2014
Abstract	Analysis of the CO2 adsorption properties of a well-known series of metal–organic frameworks M2(dobdc) (dobdc4− = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO2 adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO2 within many of these materials while systematically varying both the amount of CO2 and the temperature. Unlike previous studies, we show that CO2 adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO2 adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO2. For the weaker CO2 adsorbents, significant elongation of the metal–O(CO2) distances are observed and diffraction experiments additionally reveal that secondary CO2 adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contribute to adsorption behavior at ambient temperature. Density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO2 angles and trends in relative geometric properties and heats of adsorption in the M2(dobdc)–CO2 adducts.
Starting Page	4569
Ending Page	4581
Page Count	13
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	12
Journal	Chemical Science
DOI	10.1039/c4sc02064b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	X-ray crystallography Cu Adsorption Density functional theory Powder diffraction Van der Waals force Molecular geometry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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