High Gravimetric and Volumetric Ammonia Capacities in Robust Metal-Organic Frameworks Prepared via Double Postsynthetic Modification

Dae Won Kim, Dong Won Kang, Minjung Kang, Doo San Choi, Hongryeol Yun, Sun Young Kim, Su Min Lee, Jung Hoon Lee, Chang Seop Hong

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)


Ammonia is a promising energy vector that can store the high energy density of hydrogen. For this reason, numerous adsorbents have been investigated as ammonia storage materials, but ammonia adsorbents with a high gravimetric/volumetric ammonia capacity that can be simultaneously regenerated in an energy-efficient manner remain underdeveloped, which hampers their practical implementation. Herein, we report Ni_acryl_TMA (TMA = thiomallic acid), an acidic group-functionalized metal-organic framework prepared via successive postsynthetic modifications of mesoporous Ni2Cl2BTDD (BTDD = bis(1H-1,2,3,-triazolo [4,5-b],-[4′,5′-i]) dibenzo[1,4]dioxin). By virtue of the densely located acid groups, Ni_acryl_TMA exhibited a top-tier gravimetric ammonia capacity of 23.5 mmol g-1and the highest ammonia storage of 0.39 g cm-3at 1 bar and 298 K. The structural integrity and ammonia storage capacity of Ni_acryl_TMA were maintained after ammonia adsorption-desorption tests over five cycles. Temperature-programmed desorption analysis revealed that the moderate strength of the interaction between the functional groups and ammonia significantly reduced the desorption temperature compared to that of the pristine framework with open metal sites. The structures of the postsynthetic modified analogues were elucidated based on Pawley/Rietveld refinement of the synchrotron powder X-ray diffraction patterns and van der Waals (vdW)-corrected density functional theory (DFT) calculations. Furthermore, the ammonia adsorption mechanism was investigated via in situ infrared and vdW-corrected DFT calculations, revealing an atypical guest-induced binding mode transformation of the integrated carboxylate. Dynamic breakthrough tests showed that Ni_acryl_TMA can selectively capture traces of ammonia under both dry and wet conditions (80% relative humidity). These results demonstrate that Ni_acryl_TMA is a superior ammonia storage/capture material.

Original languageEnglish
Pages (from-to)9672-9683
Number of pages12
JournalJournal of the American Chemical Society
Issue number22
Publication statusPublished - 2022 Jun 8

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2021R1A2B5B03086313), the Priority Research Centers Program (NRF-2019R1A6A1A11044070), and PAL. J.H.L.’s work was supported by the KIST Institutional Program (Project No. 2E31801). Computational resources provided by KISTI Supercomputing Center (Project No. KSC-2020-CRE-0189) are gratefully acknowledged.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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