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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 Lab. (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}
}

Journal Article:
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Cited by: 7 works
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Figures / Tables:

Fig. 1 Fig. 1: Stress vs. strain in percentage. Compression is shown on the left and expansion on the right side. The inset shows the ball and stick diagrams of a complex organic/inorganic glassy alloy at different stages of compression/expansion: (a) compressed with a strain of 33.75% into a metallized a-ZIF; (b)more » the equilibrium a-ZIF model and; (c) expanded a-ZIF model at a tensile strain of 37.6% with large porosity and super-soft framework.« less

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.