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Title: Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework

Abstract

Porous metal-organic framework (MOF) materials with high thermal and water stability are desirable for various adsorption based applications. Early transition metal based MOFs such as those built on zirconium metal have been well recognized for their excellent stability toward heat and/or moisture. However, the difficulty growing large single crystals makes their structural characterization challenging. Herein we report a porous Zr-MOF, [Zr6O4(OH)4(cca)6] (Zr-cca), which is assembled from zirconium and 4-carboxycinnamic acid (H2cca) under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the structure of Zr-cca is isoreticular to the prototype zirconium based MOF, UiO-66. Zr-cca shows permanent porosity upon removal of solvent molecules initially residing inside the pores, with a BET surface area of 1178 m2/g. As expected, it exhibits good thermal stability (stable up to 400 °C) and high resistance to acidity over a wide pH range. Evaluation of its gas adsorption performance on various hydrocarbons and fluorocarbons indicates that it preferentially adsorbs C3 and C4 hydrocarbons over C2 analogues. At 30°C Zr-cca takes up more than 50 wt % of perfluorohexane and the adsorption-desorption process is fully recyclable. We have compared this material with UiO-66 and studied the underlying reasons for the difference in their adsorption performance towardmore » perfluorohexane.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
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  1. Rutgers Univ., Piscataway, NJ (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1436625
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 17; Journal Issue: 4; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Hao, Wang, Qining, Teat, Simon J., Olson, David H., and Li, Jing. Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework. United States: N. p., 2017. Web. doi:10.1021/acs.cgd.7b00030.
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Wang, Hao, Wang, Qining, Teat, Simon J., Olson, David H., & Li, Jing. Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework. United States. https://doi.org/10.1021/acs.cgd.7b00030
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Wang, Hao, Wang, Qining, Teat, Simon J., Olson, David H., and Li, Jing. Wed . "Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework". United States. https://doi.org/10.1021/acs.cgd.7b00030. https://www.osti.gov/servlets/purl/1436625.
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@article{osti_1436625,
title = {Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework},
author = {Wang, Hao and Wang, Qining and Teat, Simon J. and Olson, David H. and Li, Jing},
abstractNote = {Porous metal-organic framework (MOF) materials with high thermal and water stability are desirable for various adsorption based applications. Early transition metal based MOFs such as those built on zirconium metal have been well recognized for their excellent stability toward heat and/or moisture. However, the difficulty growing large single crystals makes their structural characterization challenging. Herein we report a porous Zr-MOF, [Zr6O4(OH)4(cca)6] (Zr-cca), which is assembled from zirconium and 4-carboxycinnamic acid (H2cca) under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the structure of Zr-cca is isoreticular to the prototype zirconium based MOF, UiO-66. Zr-cca shows permanent porosity upon removal of solvent molecules initially residing inside the pores, with a BET surface area of 1178 m2/g. As expected, it exhibits good thermal stability (stable up to 400 °C) and high resistance to acidity over a wide pH range. Evaluation of its gas adsorption performance on various hydrocarbons and fluorocarbons indicates that it preferentially adsorbs C3 and C4 hydrocarbons over C2 analogues. At 30°C Zr-cca takes up more than 50 wt % of perfluorohexane and the adsorption-desorption process is fully recyclable. We have compared this material with UiO-66 and studied the underlying reasons for the difference in their adsorption performance toward perfluorohexane.},
doi = {10.1021/acs.cgd.7b00030},
journal = {Crystal Growth and Design},
number = 4,
volume = 17,
place = {United States},
year = {2017},
month = {2}
}
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https://doi.org/10.1021/acs.cgd.7b00030
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    Works referencing / citing this record:

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    • DOI: 10.1002/aoc.5448

    A general and efficient approach for tuning the crystal morphology of classical MOFs
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    Computational screening, synthesis and testing of metal–organic frameworks with a bithiazole linker for carbon dioxide capture and its green conversion into cyclic carbonates
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    • Molecular Systems Design & Engineering, Vol. 4, Issue 5
    • DOI: 10.1039/c9me00062c

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