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Title: Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures

Abstract

Here we demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3O4) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe3O4NCs and Zr6O4(OH)4(fumarate)6MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe3O4NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure.

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [1];  [3];  [3];  [3];  [4];  [1];  [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics &, Univ. of Chinese Academy of Sciences
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy, Molecular Foundry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 )
OSTI Identifier:
1476605
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 40; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Qiu, Fen, Edison, John R., Preisler, Zdenek, Zhang, Yan-Fang, Li, Guo, Pan, Aizhao, Hsu, Chih-Hao, Mattox, Tracy M., Ercius, Peter, Song, Chengyu, Bustillo, Karen, Brady, Michael A., Zaia, Edmond W., Jeong, Sohee, Neaton, Jeffrey B., Du, Shixuan, Whitelam, Stephen, and Urban, Jeffrey J. Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures. United States: N. p., 2018. Web. doi:10.1002/anie.201807776.
Qiu, Fen, Edison, John R., Preisler, Zdenek, Zhang, Yan-Fang, Li, Guo, Pan, Aizhao, Hsu, Chih-Hao, Mattox, Tracy M., Ercius, Peter, Song, Chengyu, Bustillo, Karen, Brady, Michael A., Zaia, Edmond W., Jeong, Sohee, Neaton, Jeffrey B., Du, Shixuan, Whitelam, Stephen, & Urban, Jeffrey J. Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures. United States. doi:10.1002/anie.201807776.
Qiu, Fen, Edison, John R., Preisler, Zdenek, Zhang, Yan-Fang, Li, Guo, Pan, Aizhao, Hsu, Chih-Hao, Mattox, Tracy M., Ercius, Peter, Song, Chengyu, Bustillo, Karen, Brady, Michael A., Zaia, Edmond W., Jeong, Sohee, Neaton, Jeffrey B., Du, Shixuan, Whitelam, Stephen, and Urban, Jeffrey J. Wed . "Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures". United States. doi:10.1002/anie.201807776. https://www.osti.gov/servlets/purl/1476605.
@article{osti_1476605,
title = {Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures},
author = {Qiu, Fen and Edison, John R. and Preisler, Zdenek and Zhang, Yan-Fang and Li, Guo and Pan, Aizhao and Hsu, Chih-Hao and Mattox, Tracy M. and Ercius, Peter and Song, Chengyu and Bustillo, Karen and Brady, Michael A. and Zaia, Edmond W. and Jeong, Sohee and Neaton, Jeffrey B. and Du, Shixuan and Whitelam, Stephen and Urban, Jeffrey J.},
abstractNote = {Here we demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3O4) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe3O4NCs and Zr6O4(OH)4(fumarate)6MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe3O4NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure.},
doi = {10.1002/anie.201807776},
journal = {Angewandte Chemie (International Edition)},
number = 40,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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