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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, Jinhee; Choi, Jae Sun; Hwang, Sunhyun; Yun, Won Seok; Song, Dahae; Lee, JaeDong; Jeone, 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
- Adsorption; Carbon Dioxide; Catalyst; Chemical Activation; Co2; Coordinating Solvents; Crystalline Materials; Dichloromethane; Dichloromethane Treatment; Dimethyl Sulfoxide (DMSO); Electrical Conductivity; HKUST 1; In Situ NMR; In Situ Raman; Java Programming Language; Metal Organic Framework (MOF); Metal Organic Frameworks (MOFs); Metal Sites; Metals; Methane Storage; MOFS; Multiple Coordination Exchange; N,N Dimethylformamide; Nuclear Magnetic Resonance; Open Metal Sites; Organic Solvents; Porous Materials; Room Temperature Activation; Situ NMR; Situ Raman; Surface 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
- Related Researcher
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Lee, Jae Dong
Light and Matter Theory Laboratory
-
Research Interests
Theoretical Condensed Matter Physics; Ultrafast Dynamics and Optics; Nonequilibrium Phenomena
- Files:
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- Collection:
- Department of Emerging Materials ScienceLight and Matter Theory Laboratory1. Journal Articles
ETC1. Journal Articles
Department of Emerging Materials ScienceLight and Matter Theory Laboratory1. Journal Articles
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