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Title: Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution

Given the wide-ranging potential applications of metal organic frameworks (MOFs), an emerging imperative is to understand their formation with atomic scale precision. This will aid in designing syntheses for next-generation MOFs with enhanced properties and functionalities. Major challenges are to characterize the early-stage seeds, and the pathways to framework growth, which require synthesis coupled with in situ structural characterization sensitive to nanoscale structures in solution. Here we report measurements of an in situ synthesis of a prototypical MOF, ZIF-8, utilizing synchrotron X-ray atomic pair distribution function (PDF) analysis optimized for sensitivity to dilute species, complemented by mass spectrometry, electron microscopy, and density functional theory calculations. We observe that despite rapid formation of the crystalline product, a high concentration of Zn(2-MeIm) 4(2-MeIm=2-methylimidazolate) initially forms and persists as stable clusters over long times. A secondary, amorphous phase also pervades during the synthesis, which has a structural similarity to the final ZIF-8 and may act as an intermediate to the final product.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [2] ;  [4] ;  [5] ;  [4] ; ORCiD logo [4] ; ORCiD logo [2] ;  [5] ;  [6] ; ORCiD logo [2] ; ORCiD logo [7]
  1. Columbia Univ., New York, NY (United States). Dept. of Applied Physics and Applied Mathematics
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Science Directorate
  3. Brookhaven National Laboratory (BNL), Upton, NY (United States)National Synchrotron Light Source II (NSLS-II)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). W. R. Wiley Environmental Molecular Sciences Lab.
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Science Directorate; Univ. of Washington, Seattle, WA (United States). Dept. of Materials Science and Engineering
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy & Environment Directorate
  7. Columbia Univ., New York, NY (United States). Dept. of Applied Physics and Applied Mathematics; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
Publication Date:
Report Number(s):
BNL-203353-2018-JAAM
Journal ID: ISSN 2040-3364; NANOHL; TRN: US1802290
Grant/Contract Number:
SC0012704; AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 10; Journal Issue: 9; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)National Synchrotron Light Source II (NSLS-II)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1426463

Terban, Maxwell W., Banerjee, Debasis, Ghose, Sanjit, Medasani, Bharat, Shukla, Anil, Legg, Benjamin A., Zhou, Yufan, Zhu, Zihua, Sushko, Maria L., De Yoreo, James J., Liu, Jun, Thallapally, Praveen K., and Billinge, Simon J. L.. Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution. United States: N. p., Web. doi:10.1039/C7NR07949D.
Terban, Maxwell W., Banerjee, Debasis, Ghose, Sanjit, Medasani, Bharat, Shukla, Anil, Legg, Benjamin A., Zhou, Yufan, Zhu, Zihua, Sushko, Maria L., De Yoreo, James J., Liu, Jun, Thallapally, Praveen K., & Billinge, Simon J. L.. Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution. United States. doi:10.1039/C7NR07949D.
Terban, Maxwell W., Banerjee, Debasis, Ghose, Sanjit, Medasani, Bharat, Shukla, Anil, Legg, Benjamin A., Zhou, Yufan, Zhu, Zihua, Sushko, Maria L., De Yoreo, James J., Liu, Jun, Thallapally, Praveen K., and Billinge, Simon J. L.. 2018. "Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution". United States. doi:10.1039/C7NR07949D.
@article{osti_1426463,
title = {Early stage structural development of prototypical zeolitic imidazolate framework (ZIF) in solution},
author = {Terban, Maxwell W. and Banerjee, Debasis and Ghose, Sanjit and Medasani, Bharat and Shukla, Anil and Legg, Benjamin A. and Zhou, Yufan and Zhu, Zihua and Sushko, Maria L. and De Yoreo, James J. and Liu, Jun and Thallapally, Praveen K. and Billinge, Simon J. L.},
abstractNote = {Given the wide-ranging potential applications of metal organic frameworks (MOFs), an emerging imperative is to understand their formation with atomic scale precision. This will aid in designing syntheses for next-generation MOFs with enhanced properties and functionalities. Major challenges are to characterize the early-stage seeds, and the pathways to framework growth, which require synthesis coupled with in situ structural characterization sensitive to nanoscale structures in solution. Here we report measurements of an in situ synthesis of a prototypical MOF, ZIF-8, utilizing synchrotron X-ray atomic pair distribution function (PDF) analysis optimized for sensitivity to dilute species, complemented by mass spectrometry, electron microscopy, and density functional theory calculations. We observe that despite rapid formation of the crystalline product, a high concentration of Zn(2-MeIm)4(2-MeIm=2-methylimidazolate) initially forms and persists as stable clusters over long times. A secondary, amorphous phase also pervades during the synthesis, which has a structural similarity to the final ZIF-8 and may act as an intermediate to the final product.},
doi = {10.1039/C7NR07949D},
journal = {Nanoscale},
number = 9,
volume = 10,
place = {United States},
year = {2018},
month = {2}
}