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Title: Deformation behavior of an amorphous zeolitic imidazolate framework – from a supersoft material to a complex organometallic alloy

Abstract

Zeolitic imidazolate frameworks (ZIFs)—a subset of metal–organic frameworks (MOFs)—have recently attracted immense attention. Many crystalline ZIFs (c-ZIFs) have highly porous zeolite structures that are ideal for molecular encapsulation. Recently emerging non-crystalline or amorphous ZIFs (a-ZIFs) with a similar short-range order are of interest because they can be converted from c-ZIFs for large-scale production. Here, we present a computational study of the deformation behavior of a unique a-ZIF model by simulating step-wise compression and expansion with strains between –0.389 and +0.376. An insulator-to-metal transition is observed at 51 GPa leading to a multicomponent light amorphous alloy of only 3.68 g (cm) –3. A high-density amorphous-to-amorphous phase transition is observed due to the sudden formation of N–N bond pairs. Here, the systematic expansion of the a-ZIF retains the framework softness until it fractures at high strain. Based on the expansion data, we propose an empirical formula for super-soft materials, which is in line with available experimental data.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Missouri – Kansas City, Kansas City, MO (United States)
  2. Wuhan Univ. of Technology, Wuhan (People's Republic of China)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543798
Grant/Contract Number:  
AC03-76SF00098
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 46; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemistry; Physics

Citation Formats

Adhikari, Puja, Li, Neng, Rulis, Paul, and Ching, Wai -Yim. Deformation behavior of an amorphous zeolitic imidazolate framework – from a supersoft material to a complex organometallic alloy. United States: N. p., 2018. Web. doi:10.1039/c8cp05610b.
Adhikari, Puja, Li, Neng, Rulis, Paul, & Ching, Wai -Yim. Deformation behavior of an amorphous zeolitic imidazolate framework – from a supersoft material to a complex organometallic alloy. United States. doi:10.1039/c8cp05610b.
Adhikari, Puja, Li, Neng, Rulis, Paul, and Ching, Wai -Yim. Thu . "Deformation behavior of an amorphous zeolitic imidazolate framework – from a supersoft material to a complex organometallic alloy". United States. doi:10.1039/c8cp05610b. https://www.osti.gov/servlets/purl/1543798.
@article{osti_1543798,
title = {Deformation behavior of an amorphous zeolitic imidazolate framework – from a supersoft material to a complex organometallic alloy},
author = {Adhikari, Puja and Li, Neng and Rulis, Paul and Ching, Wai -Yim},
abstractNote = {Zeolitic imidazolate frameworks (ZIFs)—a subset of metal–organic frameworks (MOFs)—have recently attracted immense attention. Many crystalline ZIFs (c-ZIFs) have highly porous zeolite structures that are ideal for molecular encapsulation. Recently emerging non-crystalline or amorphous ZIFs (a-ZIFs) with a similar short-range order are of interest because they can be converted from c-ZIFs for large-scale production. Here, we present a computational study of the deformation behavior of a unique a-ZIF model by simulating step-wise compression and expansion with strains between –0.389 and +0.376. An insulator-to-metal transition is observed at 51 GPa leading to a multicomponent light amorphous alloy of only 3.68 g (cm)–3. A high-density amorphous-to-amorphous phase transition is observed due to the sudden formation of N–N bond pairs. Here, the systematic expansion of the a-ZIF retains the framework softness until it fractures at high strain. Based on the expansion data, we propose an empirical formula for super-soft materials, which is in line with available experimental data.},
doi = {10.1039/c8cp05610b},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 46,
volume = 20,
place = {United States},
year = {2018},
month = {10}
}

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Works referenced in this record:

Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999


A general phase-transfer protocol for metal ions and its application in nanocrystal synthesis
journal, July 2009

  • Yang, Jun; Sargent, Edward; Kelley, Shana
  • Nature Materials, Vol. 8, Issue 8, p. 683-689
  • DOI: 10.1038/nmat2490

Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

Metal–Organic Frameworks as Efficient Materials for Drug Delivery
journal, September 2006

  • Horcajada, Patricia; Serre, Christian; Vallet-Regí, María
  • Angewandte Chemie International Edition, Vol. 45, Issue 36, p. 5974-5978
  • DOI: 10.1002/anie.200601878

BioMOFs: Metal-Organic Frameworks for Biological and Medical Applications
journal, July 2010

  • McKinlay, Alistair C.; Morris, Russell E.; Horcajada, Patricia
  • Angewandte Chemie International Edition, Vol. 49, Issue 36, p. 6260-6266
  • DOI: 10.1002/anie.201000048

Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Enantioselective catalysis with homochiral metal–organic frameworks
journal, January 2009

  • Ma, Liqing; Abney, Carter; Lin, Wenbin
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1248-1256
  • DOI: 10.1039/b807083k

Soft porous crystals
journal, November 2009

  • Horike, Satoshi; Shimomura, Satoru; Kitagawa, Susumu
  • Nature Chemistry, Vol. 1, Issue 9, p. 695-704
  • DOI: 10.1038/nchem.444

Hybrid porous solids past, present, future
journal, January 2008

  • Férey, Gérard
  • Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
  • DOI: 10.1039/B618320B

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Single-crystal structure validation with the program PLATON
journal, January 2003