Kinetics and Mechanisms of ZnO to ZIF‐8 Transformations in Supercritical CO2 Revealed by In Situ X‐ray Diffraction

Michael A. Sinnwell; Quin R. S. Miller; Lili Liu; Jinhui Tao; Mark E. Bowden; Libor Kovarik; Dushyant Barpaga; Yi Han; Radha Kishan Motkuri; Maria L. Sushko; Herbert T. Schaef; Praveen K. Thallapally

doi:10.1002/cssc.202000434

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$Kinetics and Mechanisms of ZnO to ZIF‐8 Transformations in Supercritical CO2 Revealed by In Situ X‐ray Diffraction$

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Kinetics and Mechanisms of ZnO to ZIF‐8 Transformations in Supercritical CO2 Revealed by In Situ X‐ray Diffraction

Michael A. Sinnwell, Quin R. S. Miller, Lili Liu, Jinhui Tao, Mark E. Bowden, Libor Kovarik, Dushyant Barpaga, Yi Han, Radha Kishan Motkuri, Maria L. Sushko, …

ChemSusChem, Vol.13(10), pp.2602-2612

05/22/2020

DOI: 10.1002/cssc.202000434

PMID: 32227672

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https://www.osti.gov/biblio/1617543View

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Abstract

ZIF‐8 was synthesized in supercritical carbon dioxide (scCO2). In situ powder X‐ray diffraction, ex situ microscopy, and simulations provide an encompassing view of the formation of ZIF‐8 and intermediary ZnO@ZIF‐8 composites in this nontraditional solvent. Time‐resolved imaging exposed divergent physicochemical reaction pathways from previous studies of the growth of anisotropic ZIF‐8 core@shell structures in traditional solvents. Synthetically relevant physiochemical properties of scCO2 were integrated into classical nucleation theory, relating interfacial forces, calculated through DFTB+ based molecular dynamics (MD), with 3D nucleation outcomes. The kinetics of crystallization were examined and displayed a characteristic signature of time‐ and temperature‐dependent mechanisms over the extent of the reaction. Lastly, it is shown that subtle factors, such as the extent of reaction and the size/shape of sacrificial templates can tailor ZIF‐8 composition and size, eliciting control over hierarchical porosity in a nonconventional green solvent. Following ZIF formation: The formation of ZIF‐8 in supercritical CO2 was monitored by in situ powder X‐ray diffraction. Combined with microscopy, simulations, and kinetics analysis, an encompassing view of the green synthesis of a prototypical metal–organic framework and intermediary composites is provided. It is shown that subtle factors, such as the extent of reaction and the size/shape of templating ZnO, can tailor ZIF‐8 composition and size, eliciting control over hierarchical porosity.

green synthesis

metal–organic frameworks

nanoscale heterostructures

supercritical carbon dioxide

X-ray diffraction

Details

Title: Subtitle: Kinetics and Mechanisms of ZnO to ZIF‐8 Transformations in Supercritical CO2 Revealed by In Situ X‐ray Diffraction
Creators: Michael A. Sinnwell - Pacific Northwest National Laboratory
Quin R. S. Miller - Pacific Northwest National Laboratory
Lili Liu - Pacific Northwest National Laboratory
Jinhui Tao - Pacific Northwest National Laboratory
Mark E. Bowden - Environmental Molecular Sciences Laboratory
Libor Kovarik - Pacific Northwest National Laboratory
Dushyant Barpaga - Pacific Northwest National Laboratory
Yi Han - Qingdao University of Science and Technology
Radha Kishan Motkuri - Pacific Northwest National Laboratory
Maria L. Sushko - Pacific Northwest National Laboratory
Herbert T. Schaef - Pacific Northwest National Laboratory
Praveen K. Thallapally - Pacific Northwest National Laboratory
Resource Type: Journal article
Publication Details: ChemSusChem, Vol.13(10), pp.2602-2612
DOI: 10.1002/cssc.202000434
PMID: 32227672
NLM abbreviation: ChemSusChem
ISSN: 1864-5631
eISSN: 1864-564X
Number of pages: 11
Grant note: Basic Energy Sciences (KC020105-FWP12152)
Language: English
Date published: 05/22/2020
Academic Unit: Chemistry
Record Identifier: 9984936506602771

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