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Multiple Coordination Exchanges for Room-Temperature Activation of Open-Metal Sites in Metal-Organic Frameworks

Title
Multiple Coordination Exchanges for Room-Temperature Activation of Open-Metal Sites in Metal-Organic Frameworks
Authors
Bae, JinheeChoi, Jae SunHwang, SunhyunYun, Won SeokSong, DahaeLee, JaeDongJeone, Nak Cheon
DGIST Authors
Choi, Jae Sun; Hwang, Sunhyun; Yun, Won Seok; Song, Dahae; Lee, JaeDong; Jeone, Nak Cheon
Issue Date
2017-07
Citation
ACS Applied Materials and Interfaces, 9(29), 24743-24752
Type
Article
Article Type
Article
Keywords
AdsorptionCarbon DioxideCatalystChemical ActivationCo2Coordinating SolventsCrystalline MaterialsDichloromethaneDichloromethane TreatmentDimethyl Sulfoxide (DMSO)Electrical ConductivityHKUST 1In Situ NMRIn Situ RamanJava Programming LanguageMetal Organic Framework (MOF)Metal Organic Frameworks (MOFs)Metal SitesMetalsMethane StorageMOFSMultiple Coordination ExchangeN,N DimethylformamideNuclear Magnetic ResonanceOpen Metal SitesOrganic SolventsPorous MaterialsRoom Temperature ActivationSitu NMRSitu RamanSurface Area
ISSN
1944-8244
Abstract
The activation of open coordination sites (OCSs) in metal-organic frameworks (MOFs), i.e., the removal of solvent molecules coordinated at the OCSs, is an essential step that is required prior to the use of MOFs in potential applications such as gas chemisorption, separation, and catalysis because OCSs often serve as key sites in these applications. Recently, we developed a "chemical activation" method involving dichloromethane (DCM) treatment at room temperature, which is considered to be a promising alternative to conventional thermal activation (TA), because it does not require the application of external thermal energy, thereby preserving the structural integrity of the MOFs. However, strongly coordinating solvents such as N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), and dimethyl sulfoxide (DMSO) are difficult to remove solely with the DCM treatment. In this report, we demonstrate a multiple coordination exchange (CE) process executed initially with acetonitrile (MeCN), methanol (MeOH), or ethanol (EtOH) and subsequently with DCM to achieve the complete activation of OCSs that possess strong extracoordination. Thus, this process can serve as an effective "chemical route" to activation at room temperature that does not require applying heat. To the best of our knowledge, no previous study has demonstrated the activation of OCSs using this multiple CE process, although MeOH and/or DCM has been popularly used in pretreatment steps prior to the TA process. Using MOF-74(Ni), we demonstrate that this multiple CE process can safely activate a thermally unstable MOF without inflicting structural damage. Furthermore, on the basis of in situ 1H nuclear magnetic resonance (1H NMR) and Raman studies, we propose a plausible mechanism for the activation behavior of multiple CE. © 2017 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/4448
DOI
10.1021/acsami.7b07299
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceETC1. Journal Articles
ETC1. Journal Articles
Emerging Materials ScienceLight and Matter Theory Laboratory1. Journal Articles
Emerging Materials ScienceETC1. Journal Articles


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