Journal article
CO2 induced phase transitions in diamine-appended metal-organic frameworks
Chemical science (Cambridge), Vol.6(9), pp.5177-5185
09/01/2015
DOI: 10.1039/c5sc01828e
PMCID: PMC5500831
PMID: 28717499
Abstract
Using a combination of density functional theory and lattice models, we study the effect of CO2 adsorption in an amine functionalized metal-organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. Herein we demonstrate via quantum chemical calculations that the amines should not be considered firmly anchored to the framework and we explore the mechanism for CO2 adsorption. An ammonium carbamate species is formed via the insertion of CO2 into the M-Namine bonds. Furthermore, we translate the quantum chemical results into isotherms using a coarse grained Monte Carlo simulation technique and show that this adsorption mechanism can explain the characteristic step observed in the experimental isotherm while a previously proposed mechanism cannot. Furthermore, metal analogues have been explored and the CO2 binding energies show a strong metal dependence corresponding to the M-Namine bond strength. We show that this difference can be exploited to tune the pressure at which the step in the isotherm occurs. Additionally, the mmen-Ni-2(dobpdc) framework shows Langmuir like behavior, and our simulations show how this can be explained by competitive adsorption between the new model and a previously proposed model.
Details
- Title: Subtitle
- CO2 induced phase transitions in diamine-appended metal-organic frameworks
- Creators
- Bess Vlaisavljevich - University of California, BerkeleySamuel O. Odoh - University of MinnesotaSondre K. Schnell - University of California, BerkeleyAllison L. Dzubak - University of Minnesota SystemKyuho Lee - Lawrence Berkeley National LaboratoryNora Planas - University of MinnesotaJeffrey B. Neaton - Lawrence Berkeley National LaboratoryLaura Gagliardi - University of MinnesotaBerend Smit - Lawrence Berkeley National Laboratory
- Resource Type
- Journal article
- Publication Details
- Chemical science (Cambridge), Vol.6(9), pp.5177-5185
- Publisher
- Royal Soc Chemistry
- DOI
- 10.1039/c5sc01828e
- PMID
- 28717499
- PMCID
- PMC5500831
- ISSN
- 2041-6520
- eISSN
- 2041-6539
- Number of pages
- 9
- Grant note
- 230534 / Research Council of Norway DE-FG02-84712ER16362 / Nanoporous Materials Genome Center - U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences DE-SC0001015 / Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences; United States Department of Energy (DOE) DE-AC02-05CH11231 / Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy; United States Department of Energy (DOE) DE-AC02-05CH11231 / Office of Science of the U.S. Department of Energy; United States Department of Energy (DOE)
- Language
- English
- Date published
- 09/01/2015
- Academic Unit
- Chemistry
- Record Identifier
- 9984618632302771
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