skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films

Abstract

Here we show that sub-micron coatings of zeolitic imidazolate frameworks (ZIFs) and even ZIF–ZIF bilayers can be grown directly on polymers of intrinsic microporosity from zinc oxide (ZnO) nanocrystal precursor films, yielding a new class of all-microporous layered hybrids. The ZnO-to-ZIF chemical transformation proceeded in less than 30 min under microwave conditions using a solution of the imidazole ligand in N,N-dimethylformamide (DMF), water, or mixtures thereof. By varying the ratio of DMF to water, it was possible to control the morphology of the ZIF-on-polymer from isolated crystallites to continuous films. Grazing incidence X-ray diffraction was used to confirm the presence of crystalline ZIF in the thin films, and X-ray absorption spectroscopy was used to quantify film purity, revealing films with little to no residual ZnO. The role solvent plays in the transformation mechanism is discussed in light of these findings, which suggest the ZnO nanocrystals may be necessary to localize heterogeneous nucleation of the ZIF to the polymer surface.

Authors:
; ;  [1]; ; ; ;  [2];
  1. Department Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH 1051 Sion, Switzerland
  2. McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1386962
DOE Contract Number:  
SC0001015
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 22; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Meckler, Stephen M., Li, Changyi, Queen, Wendy L., Williams, Teresa E., Long, Jeffrey R., Buonsanti, Raffaella, Milliron, Delia J., and Helms, Brett A. Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films. United States: N. p., 2015. Web. doi:10.1021/acs.chemmater.5b03219.
Meckler, Stephen M., Li, Changyi, Queen, Wendy L., Williams, Teresa E., Long, Jeffrey R., Buonsanti, Raffaella, Milliron, Delia J., & Helms, Brett A. Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films. United States. doi:10.1021/acs.chemmater.5b03219.
Meckler, Stephen M., Li, Changyi, Queen, Wendy L., Williams, Teresa E., Long, Jeffrey R., Buonsanti, Raffaella, Milliron, Delia J., and Helms, Brett A. Mon . "Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films". United States. doi:10.1021/acs.chemmater.5b03219.
@article{osti_1386962,
title = {Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films},
author = {Meckler, Stephen M. and Li, Changyi and Queen, Wendy L. and Williams, Teresa E. and Long, Jeffrey R. and Buonsanti, Raffaella and Milliron, Delia J. and Helms, Brett A.},
abstractNote = {Here we show that sub-micron coatings of zeolitic imidazolate frameworks (ZIFs) and even ZIF–ZIF bilayers can be grown directly on polymers of intrinsic microporosity from zinc oxide (ZnO) nanocrystal precursor films, yielding a new class of all-microporous layered hybrids. The ZnO-to-ZIF chemical transformation proceeded in less than 30 min under microwave conditions using a solution of the imidazole ligand in N,N-dimethylformamide (DMF), water, or mixtures thereof. By varying the ratio of DMF to water, it was possible to control the morphology of the ZIF-on-polymer from isolated crystallites to continuous films. Grazing incidence X-ray diffraction was used to confirm the presence of crystalline ZIF in the thin films, and X-ray absorption spectroscopy was used to quantify film purity, revealing films with little to no residual ZnO. The role solvent plays in the transformation mechanism is discussed in light of these findings, which suggest the ZnO nanocrystals may be necessary to localize heterogeneous nucleation of the ZIF to the polymer surface.},
doi = {10.1021/acs.chemmater.5b03219},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 22,
volume = 27,
place = {United States},
year = {2015},
month = {11}
}