Unusually large band gap changes in breathing metal–organic framework materials

Ling, Sanliang; Slater, Ben

Abstract

Many of the potential applications for metal–organic frameworks (MOFs) focus on exploiting their porosity for molecular storage, release, and separation, where the functional behavior is controlled by a subtle balance of host–guest interactions. Typically, the host structure is relatively unperturbed by the presence of guests; however, a subset of MOFs exhibit dramatic phase-change behavior triggered by the adsorption of guests or other stimuli, for which the MIL-53 material is an archetype. In this work, we use density functional approaches to examine the electronic structure changes associated with changes of phase and density and find the associated change in band gaps can be larger than 1 eV for known MIL-53-type materials and hypothecated structures. Moreover, we show that internal pressure (via guest molecules) and external pressure can exert a major influence on the band gap size and gap states. The large response in electronic properties to breathing transitions in MOFs could be exploitable in future applications in resistive switching, phase-change memory, piezoresistor, gas-sensing and thermochromic materials.

Citation

Ling, S., & Slater, B. (2015). Unusually large band gap changes in breathing metal–organic framework materials. Journal of Physical Chemistry C, 119(29), 16667-16677. https://doi.org/10.1021/acs.jpcc.5b04050

• Journal Article Type: Article
• Acceptance Date: Jun 22, 2015
• Online Publication Date: Jun 23, 2015
• Publication Date: Jul 23, 2015
• Deposit Date: Nov 20, 2018
• Journal: The Journal of Physical Chemistry C
• Print ISSN: 1932-7447
• Electronic ISSN: 1932-7455
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 119
• Issue: 29
• Pages: 16667-16677
• DOI: https://doi.org/10.1021/acs.jpcc.5b04050
• Public URL: https://nottingham-repository.worktribe.com/output/1288077
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.jpcc.5b04050