Issue 9, 2019

Geometry and energetics of CO adsorption on hydroxylated UiO-66

Abstract

The metal–organic framework (MOF), UiO-66, contains Brønsted acidic and Lewis acidic sites that play an important role in sorption, separation, and potential catalytic processes involving small gaseous molecules. As such, studies into the sequestration and separation of CO within UiO-66 provides a fundamental understanding of small gas molecule adsorption within a highly porous, tunable and environmentally stable MOF. Infrared spectroscopic measurements, in combination with density functional theory, were employed to characterize the binding energetics between bridging hydroxyl groups at MOF nodes and the adsorbate, CO. Two unique binding configurations between CO and the μ3-OH groups were identified based on differing stretching vibrations of COads when interacting through the C- and O-atom of the molecule. Variable temperature infrared spectroscopy (VTIR) was employed to attain energetics of CO adsorption (−17 kJ mol−1) and isomerization from the carbonyl to the isocarbonyl configuration (4 kJ mol−1). Results suggest that CO–hydroxyl interactions, while weak in nature, play a critical role in CO adsorption within the confined pore environment of UiO-66.

Graphical abstract: Geometry and energetics of CO adsorption on hydroxylated UiO-66

Article information

Article type
Paper
Submitted
20 Dec 2018
Accepted
05 Feb 2019
First published
05 Feb 2019

Phys. Chem. Chem. Phys., 2019,21, 5078-5085

Author version available

Geometry and energetics of CO adsorption on hydroxylated UiO-66

D. M. Driscoll, D. Troya, P. M. Usov, A. J. Maynes, A. J. Morris and J. R. Morris, Phys. Chem. Chem. Phys., 2019, 21, 5078 DOI: 10.1039/C8CP07778A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements