Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO2Adsorption

Doo San Choi; Dae Won Kim; Jung Hoon Lee; Yun Seok Chae; Dong Won Kang; Chang Seop Hong

doi:10.1021/acsami.1c10659

Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO₂Adsorption

Doo San Choi
, Dae Won Kim
, Jung Hoon Lee
, Yun Seok Chae
, Dong Won Kang
, Chang Seop Hong^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	38358-38364
Number of pages	7
Journal	ACS Applied Materials and Interfaces
Volume	13
Issue number	32
DOIs	https://doi.org/10.1021/acsami.1c10659
Publication status	Published - 2021 Aug 18

Bibliographical note

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:
©

Keywords

carbon dioxide capture
diamine functionalization
metal-organic frameworks
solvent exchange
solvent polarity

ASJC Scopus subject areas

General Materials Science

Access to Document

10.1021/acsami.1c10659

Cite this

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title = "Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO2Adsorption",

abstract = "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. ",

keywords = "carbon dioxide capture, diamine functionalization, metal-organic frameworks, solvent exchange, solvent polarity",

author = "Choi, \{Doo San\} and Kim, \{Dae Won\} and Lee, \{Jung Hoon\} and Chae, \{Yun Seok\} and Kang, \{Dong Won\} and Hong, \{Chang Seop\}",

note = "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: {\textcopyright} ",

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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

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