---
_id: '7301'
abstract:
- lang: eng
text: Several problems arise at the O2 (positive) electrode in the Li-air battery,
including solvent/electrode decomposition and electrode passivation by insulating
Li2O2. Progress partially depends on exploring the basic electrochemistry of O2
reduction. Here we describe the effect of complexing-cations on the electrochemical
reduction of O2 in DMSO in the presence and absence of a Li salt. The solubility
of alkaline peroxides in DMSO is enhanced by the complexing-cations, consistent
with their strong interaction with reduced O2. The complexing-cations also increase
the rate of the 1-electron O2 reduction to O2•– by up to six-fold (k° = 2.4 ×10–3
to 1.5 × 10–2 cm s–1) whether or not Li+ ions are present. In the absence of Li+,
the complexing-cations also promote the reduction of O2•– to O22–. In the presence
of Li+ and complexing-cations, and despite the interaction of the reduced O2 with
the latter, SERS confirms that the product is still Li2O2.
article_processing_charge: No
article_type: original
author:
- first_name: Chunmei
full_name: Li, Chunmei
last_name: Li
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Lee
full_name: Johnson, Lee
last_name: Johnson
- first_name: Sylvie
full_name: Grugeon, Sylvie
last_name: Grugeon
- first_name: Stéphane
full_name: Laruelle, Stéphane
last_name: Laruelle
- first_name: Peter G.
full_name: Bruce, Peter G.
last_name: Bruce
- first_name: Michel
full_name: Armand, Michel
last_name: Armand
citation:
ama: 'Li C, Fontaine O, Freunberger SA, et al. Aprotic Li–O2 battery: Influence
of complexing agents on oxygen reduction in an aprotic solvent. The Journal
of Physical Chemistry C. 2014;118(7):3393-3401. doi:10.1021/jp4093805'
apa: 'Li, C., Fontaine, O., Freunberger, S. A., Johnson, L., Grugeon, S., Laruelle,
S., … Armand, M. (2014). Aprotic Li–O2 battery: Influence of complexing agents
on oxygen reduction in an aprotic solvent. The Journal of Physical Chemistry
C. ACS. https://doi.org/10.1021/jp4093805'
chicago: 'Li, Chunmei, Olivier Fontaine, Stefan Alexander Freunberger, Lee Johnson,
Sylvie Grugeon, Stéphane Laruelle, Peter G. Bruce, and Michel Armand. “Aprotic
Li–O2 Battery: Influence of Complexing Agents on Oxygen Reduction in an Aprotic
Solvent.” The Journal of Physical Chemistry C. ACS, 2014. https://doi.org/10.1021/jp4093805.'
ieee: 'C. Li et al., “Aprotic Li–O2 battery: Influence of complexing agents
on oxygen reduction in an aprotic solvent,” The Journal of Physical Chemistry
C, vol. 118, no. 7. ACS, pp. 3393–3401, 2014.'
ista: 'Li C, Fontaine O, Freunberger SA, Johnson L, Grugeon S, Laruelle S, Bruce
PG, Armand M. 2014. Aprotic Li–O2 battery: Influence of complexing agents on oxygen
reduction in an aprotic solvent. The Journal of Physical Chemistry C. 118(7),
3393–3401.'
mla: 'Li, Chunmei, et al. “Aprotic Li–O2 Battery: Influence of Complexing Agents
on Oxygen Reduction in an Aprotic Solvent.” The Journal of Physical Chemistry
C, vol. 118, no. 7, ACS, 2014, pp. 3393–401, doi:10.1021/jp4093805.'
short: C. Li, O. Fontaine, S.A. Freunberger, L. Johnson, S. Grugeon, S. Laruelle,
P.G. Bruce, M. Armand, The Journal of Physical Chemistry C 118 (2014) 3393–3401.
date_created: 2020-01-15T12:17:28Z
date_published: 2014-01-29T00:00:00Z
date_updated: 2021-01-12T08:12:53Z
day: '29'
doi: 10.1021/jp4093805
extern: '1'
intvolume: ' 118'
issue: '7'
language:
- iso: eng
month: '01'
oa_version: None
page: 3393-3401
publication: The Journal of Physical Chemistry C
publication_identifier:
issn:
- 1932-7447
- 1932-7455
publication_status: published
publisher: ACS
quality_controlled: '1'
status: public
title: 'Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction
in an aprotic solvent'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 118
year: '2014'
...
---
_id: '6370'
abstract:
- lang: eng
text: 'The molecular and supramolecular origins of the superior nonlinear optical
(NLO) properties observed in the organic phenolic triene material, OH1 (2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile),
are presented. The molecular charge-transfer distribution is topographically mapped,
demonstrating that a uniformly delocalized passive electronic medium facilitates
the charge-transfer between the phenolic electron donor and the cyano electron
acceptors which lie at opposite ends of the molecule. Its ability to act as a
“push–pull” π-conjugated molecule is quantified, relative to similar materials,
by supporting empirical calculations; these include bond-length alternation and
harmonic-oscillator stabilization energy (HOSE) tests. Such tests, together with
frontier molecular orbital considerations, reveal that OH1 can exist readily in
its aromatic (neutral) or quinoidal (charge-separated) state, thereby overcoming
the “nonlinearity-thermal stability trade-off”. The HOSE calculation also reveals
a correlation between the quinoidal resonance contribution to the overall structure
of OH1 and the UV–vis absorption peak wavelength in the wider family of configurationally
locked polyene framework materials. Solid-state tensorial coefficients of the
molecular dipole, polarizability, and the first hyperpolarizability for OH1 are
derived from the first-, second-, and third-order electronic moments of the experimental
charge-density distribution. The overall solid-state molecular dipole moment is
compared with those from gas-phase calculations, revealing that crystal field
effects are very significant in OH1. The solid-state hyperpolarizability derived
from this charge-density study affords good agreement with gas-phase calculations
as well as optical measurements based on hyper-Rayleigh scattering (HRS) and electric-field-induced
second harmonic (EFISH) generation. This lends support to the further use of charge-density
studies to calculate solid-state hyperpolarizability coefficients in other organic
NLO materials. Finally, this charge-density study is also employed to provide
an advanced classification of hydrogen bonds in OH1, which requires more stringent
criteria than those from conventional structure analysis. As a result, only the
strongest OH···NC interaction is so classified as a true hydrogen bond. Indeed,
it is this electrostatic interaction that influences the molecular charge transfer:
the other four, weaker, nonbonded contacts nonetheless affect the crystal packing.
Overall, the establishment of these structure–property relationships lays a blueprint
for designing further, more NLO efficient, materials in this industrially leading
organic family of compounds.'
author:
- first_name: Tze-Chia
full_name: Lin, Tze-Chia
last_name: Lin
- first_name: Jacqueline M.
full_name: Cole, Jacqueline M.
last_name: Cole
- first_name: Andrew P
full_name: Higginbotham, Andrew P
id: 4AD6785A-F248-11E8-B48F-1D18A9856A87
last_name: Higginbotham
orcid: 0000-0003-2607-2363
- first_name: Alison J.
full_name: Edwards, Alison J.
last_name: Edwards
- first_name: Ross O.
full_name: Piltz, Ross O.
last_name: Piltz
- first_name: Javier
full_name: Pérez-Moreno, Javier
last_name: Pérez-Moreno
- first_name: Ji-Youn
full_name: Seo, Ji-Youn
last_name: Seo
- first_name: Seung-Chul
full_name: Lee, Seung-Chul
last_name: Lee
- first_name: Koen
full_name: Clays, Koen
last_name: Clays
- first_name: O-Pil
full_name: Kwon, O-Pil
last_name: Kwon
citation:
ama: 'Lin T-C, Cole JM, Higginbotham AP, et al. Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of
Physical Chemistry C. 2013;117(18):9416-9430. doi:10.1021/jp400648q'
apa: 'Lin, T.-C., Cole, J. M., Higginbotham, A. P., Edwards, A. J., Piltz, R. O.,
Pérez-Moreno, J., … Kwon, O.-P. (2013). Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of
Physical Chemistry C. American Chemical Society (ACS). https://doi.org/10.1021/jp400648q'
chicago: 'Lin, Tze-Chia, Jacqueline M. Cole, Andrew P Higginbotham, Alison J. Edwards,
Ross O. Piltz, Javier Pérez-Moreno, Ji-Youn Seo, Seung-Chul Lee, Koen Clays, and
O-Pil Kwon. “Molecular Origins of the High-Performance Nonlinear Optical Susceptibility
in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding,
and Ab Initio Calculations.” The Journal of Physical Chemistry C. American
Chemical Society (ACS), 2013. https://doi.org/10.1021/jp400648q.'
ieee: 'T.-C. Lin et al., “Molecular origins of the high-performance nonlinear
optical susceptibility in a phenolic polyene chromophore: Electron density distributions,
hydrogen bonding, and ab initio calculations,” The Journal of Physical Chemistry
C, vol. 117, no. 18. American Chemical Society (ACS), pp. 9416–9430, 2013.'
ista: 'Lin T-C, Cole JM, Higginbotham AP, Edwards AJ, Piltz RO, Pérez-Moreno J,
Seo J-Y, Lee S-C, Clays K, Kwon O-P. 2013. Molecular origins of the high-performance
nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density
distributions, hydrogen bonding, and ab initio calculations. The Journal of Physical
Chemistry C. 117(18), 9416–9430.'
mla: 'Lin, Tze-Chia, et al. “Molecular Origins of the High-Performance Nonlinear
Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions,
Hydrogen Bonding, and Ab Initio Calculations.” The Journal of Physical Chemistry
C, vol. 117, no. 18, American Chemical Society (ACS), 2013, pp. 9416–30, doi:10.1021/jp400648q.'
short: T.-C. Lin, J.M. Cole, A.P. Higginbotham, A.J. Edwards, R.O. Piltz, J. Pérez-Moreno,
J.-Y. Seo, S.-C. Lee, K. Clays, O.-P. Kwon, The Journal of Physical Chemistry
C 117 (2013) 9416–9430.
date_created: 2019-05-03T09:40:31Z
date_published: 2013-05-09T00:00:00Z
date_updated: 2021-01-12T08:07:17Z
day: '09'
doi: 10.1021/jp400648q
extern: '1'
intvolume: ' 117'
issue: '18'
language:
- iso: eng
month: '05'
oa_version: None
page: 9416-9430
publication: The Journal of Physical Chemistry C
publication_identifier:
issn:
- 1932-7447
- 1932-7455
publication_status: published
publisher: American Chemical Society (ACS)
quality_controlled: '1'
status: public
title: 'Molecular origins of the high-performance nonlinear optical susceptibility
in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding,
and ab initio calculations'
type: journal_article
user_id: 3E5EF7F0-F248-11E8-B48F-1D18A9856A87
volume: 117
year: '2013'
...