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

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


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 languageEnglish
Pages (from-to)38358-38364
Number of pages7
JournalACS Applied Materials and Interfaces
Issue number32
Publication statusPublished - 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:


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

ASJC Scopus subject areas

  • General Materials Science


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