Metal-to-Semiconductor Transition in Two-Dimensional Metal-Organic Frameworks: An Ab Initio Dynamics Perspective
Document Type
Article
Publication Date
6-2-2021
Abstract
Two-dimensional (2D) π-stacked layered metal-organic frameworks (MOFs) are permanently porous and electrically conductive materials with easily tunable crystal structures. Here, we provide an accurate examination of the correlation between structural features and electronic properties of Ni3(HITP)2, HITP = 2,3,6,7,10,11-hexaiminotriphenylene, as an archetypical 2D MOF. The main objective of this work is to unravel the responsive nature of the layered architecture to external stimuli such as temperature and show how the layer flexibility translates to different conductive behaviors. To this end, we employ a combination of quantum mechanical tools, ab initio molecular dynamics (AIMD) simulations, and electronic band structure calculations. We compare the band structure and projected density of states of equilibrated system at 293 K to that of the 0 K optimized structure. Effect of interlayer π-π and intralayer d−π interactions on charge mobility is disentangled and studied by increasing the distance between layers of Ni3(HITP)2 and comparison to an exemplary case of Zn3(HITP)2 2D MOF. Our findings show how a structural change, which can be deformations along the layers, slipping of layers, or change of the interlayer distance, can induce metal-to-semiconductor or indirect-to-direct semiconductor transition, suggesting a way to adjust or even switch between the intralayer vs interlayer conductive anisotropy in Ni3(HITP)2, in particular, and 2D MOFs in general.
Identifier
85107711016 (Scopus)
Publication Title
ACS Applied Materials and Interfaces
External Full Text Location
https://doi.org/10.1021/acsami.1c04636
e-ISSN
19448252
ISSN
19448244
PubMed ID
34015222
First Page
25270
Last Page
25279
Issue
21
Volume
13
Grant
CHE200007
Fund Ref
Nanjing Institute of Technology
Recommended Citation
Zhang, Zeyu; Dell’Angelo, David; Momeni, Mohammad R.; Shi, Yuliang; and Shakib, Farnaz A., "Metal-to-Semiconductor Transition in Two-Dimensional Metal-Organic Frameworks: An Ab Initio Dynamics Perspective" (2021). Faculty Publications. 4051.
https://digitalcommons.njit.edu/fac_pubs/4051
