TY - JOUR
T1 - Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO2Adsorption
AU - Choi, Doo San
AU - Kim, Dae Won
AU - Lee, Jung Hoon
AU - Chae, Yun Seok
AU - Kang, Dong Won
AU - Hong, Chang Seop
N1 - Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (NRF-2018R1A2A1A05079297) and the Priority Research Centers Program (NRF-2019R1A6A1A11044070). The authors thank the Institute for Basic Science (IBS) Center for Molecular Spectroscopy and Dynamics (IBS-R023-D1) for providing NMR spectrometry and professional technical support. J.-H.L. was supported by the KIST institutional program (Project No. 2E31201). Computational resources were provided by KISTI supercomputing center (Project No. KSC-2020-CRE-0361).
Publisher Copyright:
©
PY - 2021/8/18
Y1 - 2021/8/18
N2 - Diamine-appended metal-organic frameworks (MOFs) exhibit exceptional CO2 adsorption capacities over a wide pressure range because of the strong interaction between basic amine groups and acidic CO2. Given that their high CO2 working capacity is governed by solvent used during amine functionalization, a systematic investigation on solvent effect is essential but not yet demonstrated. Herein, we report a facile one-step solvent exchange route for the diamine functionalization of MOFs with open metal sites, using an efficient method to maximize diamine loading. We employed an MOF, Mg2(dobpdc) (dobpdc4- = 4,4′-dioxido-3,3′-biphenyldicarboxylate), which contains high-density open metal sites. Indirect grafting with N-ethylethylenediamine (een) was performed with a minimal amount of methanol (MeOH) via multiple MeOH exchanges and diamine functionalization, resulting in a top-tier CO2 adsorption capacity of 16.5 wt %. We established the correlation between N,N-dimethylformamide (DMF) loading and infrared peaks, which provides a simple method for determining the amount of the remaining DMF in Mg2(dobpdc). All interactions among Mg, DMF, diamine, and solvent were analyzed by van der Waals (vdw)-corrected density functional theory (DFT) calculations to elucidate the effect of chemical potential on diamine grafting.
AB - Diamine-appended metal-organic frameworks (MOFs) exhibit exceptional CO2 adsorption capacities over a wide pressure range because of the strong interaction between basic amine groups and acidic CO2. Given that their high CO2 working capacity is governed by solvent used during amine functionalization, a systematic investigation on solvent effect is essential but not yet demonstrated. Herein, we report a facile one-step solvent exchange route for the diamine functionalization of MOFs with open metal sites, using an efficient method to maximize diamine loading. We employed an MOF, Mg2(dobpdc) (dobpdc4- = 4,4′-dioxido-3,3′-biphenyldicarboxylate), which contains high-density open metal sites. Indirect grafting with N-ethylethylenediamine (een) was performed with a minimal amount of methanol (MeOH) via multiple MeOH exchanges and diamine functionalization, resulting in a top-tier CO2 adsorption capacity of 16.5 wt %. We established the correlation between N,N-dimethylformamide (DMF) loading and infrared peaks, which provides a simple method for determining the amount of the remaining DMF in Mg2(dobpdc). All interactions among Mg, DMF, diamine, and solvent were analyzed by van der Waals (vdw)-corrected density functional theory (DFT) calculations to elucidate the effect of chemical potential on diamine grafting.
KW - carbon dioxide capture
KW - diamine functionalization
KW - metal-organic frameworks
KW - solvent exchange
KW - solvent polarity
UR - http://www.scopus.com/inward/record.url?scp=85113315758&partnerID=8YFLogxK
U2 - 10.1021/acsami.1c10659
DO - 10.1021/acsami.1c10659
M3 - Article
C2 - 34342422
AN - SCOPUS:85113315758
VL - 13
SP - 38358
EP - 38364
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 32
ER -