Computational analysis to study the effect of infusion of Tetracyanoquinodimethane in zinc based metal-organic framework

Abstract

The present study reports the computational analysis of band structures and density of state (DOS) profiles of a Tetracyanoquinodimethane (TCNQ) infused IRMOF-1 (Iso Reticular Metal-Organic Framework-1). IRMOF-1 is a zinc-based MOF and has been reported useful in literature for a variety of applications, including gas storage and sensing owing to its highly porous structure. We have adopted a SIESTA based computational investigation approach to investigate the tuning of the band structure and DOS of IRMOF-1 via the infusion of a redox active species, i.e., TCNQ. The results have highlighted that the doping of TCNQ in IRMOF-1 is useful for the realization of a novel material with an estimated band gap of 4.35 eV. The necessary computational steps involved various optimization steps, such as the optimization of mesh-cutoff, lattice constant, lattice volume, and conjugate gradient. These computation studies have thus established that an approach of doping IRMOF-1 with TCNQ can result in the development of a suitably functional porous material that can be further exploited as an ultrawide-bandgap semiconductor material or for the electrochemical sensing of different analytes, such as gases.

Host–Guest Interactions in Metal–Organic Frameworks Doped with Acceptor Molecules as Revealed by Resonance Raman Spectroscopy

“…It was reported that the electrical conductivity of HKUST-1 can be increased by six orders of magnitude to 7 S/m by doping with 7,7,8,8-tetracyanoquinodimethane (TCNQ), a redox-active organic molecule . Since this pioneering work, much effort has been devoted to the investigation of emergent properties of TCNQ-doped HKUST-1 ,− and some other MOFs − including Co-MOF-74. , Regarding the principles governing charge transport in TCNQ-doped HKUST-1, superexchange electron transport was suggested to explain the low activation energy …”