Issue 3, 2019

Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides

Abstract

Dioxides (dioxygenyl (O2+), dioxygen (O2), superoxide (O2˙) and peroxide (O22−)) are of immense biological, chemical and environmental importance. The ability to accurately detect and measure the changing strength of their chemical bonding and coordination in situ or operando is extremely beneficial in order to evaluate their chemical properties, this has been particularly important recently in the field of metal–oxygen batteries, where understanding the reactivity of the O2˙ intermediate is crucial in the development of more stable electrolytes. Meta-analysis of the collated vibrational Raman and IR spectral bands of numerous (>200) dioxygen species was used to interpret the effect that the immediate chemical environment has on the O–O bond. Subsequently, the dioxide vibrational spectral bands were empirically related directly with the bond electron density and other fundamental bond properties, with surprisingly high accuracy, allowing each property to be estimated, simply, from experimental spectroscopic observations. Important chemical information about the strength of secondary interactions between reduced oxygen species and its chemical environment can be also elucidated which provides a convenient method for determining the attractive strength an ion exerts over neighbouring counter ions.

Graphical abstract: Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides

Supplementary files

Article information

Article type
Paper
Submitted
22 Jul 2018
Accepted
05 Nov 2018
First published
08 Jan 2019
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 1552-1563

Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides

P. M. Radjenovic and L. J. Hardwick, Phys. Chem. Chem. Phys., 2019, 21, 1552 DOI: 10.1039/C8CP04652B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements