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

Journal Article · · Nanoscale
DOI:https://doi.org/10.1039/C7NR07949D· OSTI ID:1426463
 [1];  [2];  [3];  [2];  [4];  [5];  [4];  [4];  [2];  [5];  [6];  [2];  [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.
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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.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)National Synchrotron Light Source II (NSLS-II)
Sponsoring Organization:
National Science Foundation (NSF); 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)
Grant/Contract Number:
AC05-76RL01830; SC0012704
OSTI ID:
1426463
Alternate ID(s):
OSTI ID: 1434862
Report Number(s):
BNL--203353-2018-JAAM
Journal Information:
Nanoscale, Journal Name: Nanoscale Journal Issue: 9 Vol. 10; ISSN NANOHL; ISSN 2040-3364
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Control of Metal–Organic Framework Crystallization by Metastable Intermediate Pre‐equilibrium Species journal December 2018
Control of Metal–Organic Framework Crystallization by Metastable Intermediate Pre‐equilibrium Species journal January 2019
The Chemistry of Nucleation: In Situ Pair Distribution Function Analysis of Secondary Building Units During UiO‐66 MOF Formation journal January 2019
A new experimental setup for time- and laterally-resolved X-ray absorption fine structure spectroscopy in a ‘single shot’ journal January 2019
Metal–organic framework derived Co 3 O 4 /C@SiO 2 yolk–shell nanoreactors with enhanced catalytic performance journal January 2018
Synthesis of Au nanorod-embedded and graphene oxide-wrapped microporous ZIF-8 with high electrocatalytic activity for the sensing of pesticides journal January 2019
2D molecular crystal lattices: advances in their synthesis, characterization, and application journal January 2019
The Chemistry of Nucleation: In Situ Pair Distribution Function Analysis of Secondary Building Units During UiO‐66 MOF Formation text January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY