1. Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures.
- Author
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Qiu, F, Edison, JR, Preisler, Z, Zhang, Y-F, Li, G, Pan, A, Hsu, C-H, Mattox, TM, Ercius, P, Song, C, Bustillo, K, Brady, MA, Zaia, EW, Jeong, S, Neaton, JB, Du, S, Whitelam, S, and Urban, JJ
- Subjects
Engineering ,Macromolecular and Materials Chemistry ,Materials Engineering ,Chemical Sciences ,Nanotechnology ,Bioengineering ,Affordable and Clean Energy ,DFT calculations ,MD simulations ,metal-organic frameworks ,self-assembly ,superstructure ,Organic Chemistry ,Chemical sciences - Abstract
We demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3 O4 ) 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 Fe3 O4 NCs and Zr6 O4 (OH)4 (fumarate)6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe3 O4 NCs 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.
- Published
- 2018