Tuning Gas Adsorption by Metal Node Blocking in Photoresponsive Metal–Organic Frameworks
Journal
Chemistry - A European Journal
Journal Volume
24
Journal Issue
57
Pages
15167-16172
Date Issued
2018
Author(s)
Abstract
By combining first-principles calculations and classical molecular simulations, an atomistic-level of understanding was provided towards the notable change in CO2 adsorption upon light treatment in two recently reported photoactive metal–organic frameworks, PCN-123 and Cu2(AzoBPDC)2(AzoBiPyB). It was demonstrated that the reversible decrease in gas adsorption upon isomerization can be primarily attributed to the blocking of the strong adsorbing sites at the metal nodes by azobenzene molecules in a cis configuration. The same mechanism was found to apply also to other molecules, for example, alkanes and toxic gases. Such understandings are instrumental to the future design of photoresponsive metal–organic frameworks. For example, the metal node-blocking mechanism can be leveraged to achieve optimal adsorption properties as a function of metal substitution and/or ligand functionalization. As a proof of concept, it was shown that the working capacity could be increased by a factor of two in PCN-123 by replacing the Zn4O node with the more strongly adsorbing Mg4O. ? 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Subjects
Adsorption
Calculations
Gas adsorption
Intelligent systems
Magnesium compounds
Molecules
Monte Carlo methods
Porous materials
Zinc compounds
Ab initio calculations
Adsorption properties
Azobenzene molecules
Cis configurations
First-principles calculation
Ligand functionalization
Molecular simulations
stimulus responsive MOFs
Metals
Type
journal article