Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps

Jinhui Tao; Mal-Soon Lee; Maria L Sushko; James J De Yoreo; Jun Liu; Zhisen Zhang; Debasis Banerjee; Susrut Akkineni; Mark E Bowden; Praveen K Thallapally; Yongsoon Shin; Michael A Sinnwell

doi:10.1021/acs.chemmater.0c02123

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Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps

Journal article

Peer reviewed

Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps

Jinhui Tao, Mal-Soon Lee, Maria L Sushko, James J De Yoreo, Jun Liu, Zhisen Zhang, Debasis Banerjee, Susrut Akkineni, Mark E Bowden, Praveen K Thallapally, …

Chemistry of materials, Vol.32(15), pp.6666-6675

08/11/2020

DOI: 10.1021/acs.chemmater.0c02123

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https://www.osti.gov/biblio/1686075View

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Abstract

Metal–organic framework (MOF) heterostructures exhibit unique properties beyond those of individual components, but their design requires an understanding of energetic and kinetic controls at MOF–substrate interfaces. Although the structural relationship has been widely used in heterostructure design, it overlooks the interplay between the organic ligand and the substrate which controls the kinetics and energetics of growth of the final structure. Herein we used zeolitic imidazolate frameworks (ZIF-8) on ZnO as a model system to evaluate this interplay via in situ monitoring and simulations. Our results demonstrate multiple roles of the 2-methyl-imidazole (2-MIM) ligand as “dissolution-promoter”, “step-pinner”, and “terrace-binder” on the ZnO (001) face and “dissolution-promoter” and “terrace-binder” on the ZnO (100) face. Through these multiple face-specific roles, 2-MIM modulates ZnO dissolution kinetics and, hence, the Zn2+ release rate, tuning local supersaturations that dictating the characteristic ZIF-8 crystallization kinetics on different substrate faces. The critical thickness for transition from 2D to 3D growth is dictated by competition between interfacial and strain energies. The atomic-scale mechanism of the coupled substrate dissolution and MOF growth, mediated by selective linker–substrate binding, furnishes a new synthesis pathway for other complex heterostructures.

Details

Title: Subtitle: Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps
Creators: Jinhui Tao - Pacific Northwest National Laboratory
Mal-Soon Lee - Computational Sciences (United States)
Maria L Sushko - Pacific Northwest National Laboratory
James J De Yoreo - Pacific Northwest National Laboratory
Jun Liu - University of Washington
Zhisen Zhang - Xiamen University
Debasis Banerjee - Pacific Northwest National Laboratory
Susrut Akkineni - University of Washington
Mark E Bowden - Environmental Molecular Sciences Laboratory
Praveen K Thallapally - Pacific Northwest National Laboratory
Yongsoon Shin - Pacific Northwest National Laboratory
Michael A Sinnwell - Pacific Northwest National Laboratory
Resource Type: Journal article
Publication Details: Chemistry of materials, Vol.32(15), pp.6666-6675
DOI: 10.1021/acs.chemmater.0c02123
ISSN: 0897-4756
eISSN: 1520-5002
Publisher: American Chemical Society
Number of pages: 10
Language: English
Date published: 08/11/2020
Academic Unit: Chemistry
Record Identifier: 9984936618402771

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