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Single Metal Atom Catalysts and ORR : H-Bonding, Solvation, and the Elusive Hydroperoxyl Intermediate

Armillotta, Francesco ; Bidoggia, Davide ; Baronio, Stefania ; Biasin, Pietro ; Annese, Antonio ; Scardamaglia, Mattia LU ; Zhu, Suyun LU ; Bozzini, Benedetto ; Modesti, Silvio and Peressi, Maria , et al. (2022) In ACS Catalysis 12(13). p.7950-7959
Abstract
The widely investigated oxygen reduction reaction (ORR) is well-known to
proceed via two competing routes, involving two or four electrons, and
yielding different reaction products, respectively. Both pathways are
believed to share a common, elusive intermediate, namely, the
hydroperoxyl radical. By exploiting a cobalt single-atom biomimetic
model catalyst, based on a self-assembled monolayer of Co-porphyrins
grown on an almost free-standing graphene sheet, we identify, in situ at
room temperature in O2+H2O atmosphere, a hydroperoxyl-water cluster
that is stabilized at the Co single-metal atom catalytic site. We show
that the interplay between charge transfer, dipole and... (More)
The widely investigated oxygen reduction reaction (ORR) is well-known to
proceed via two competing routes, involving two or four electrons, and
yielding different reaction products, respectively. Both pathways are
believed to share a common, elusive intermediate, namely, the
hydroperoxyl radical. By exploiting a cobalt single-atom biomimetic
model catalyst, based on a self-assembled monolayer of Co-porphyrins
grown on an almost free-standing graphene sheet, we identify, in situ at
room temperature in O2+H2O atmosphere, a hydroperoxyl-water cluster
that is stabilized at the Co single-metal atom catalytic site. We show
that the interplay between charge transfer, dipole and H-bonding, and
water solvation behavior actually determines the hydroperoxyl-water
complex stability, the Co-OOH bonding geometry, and, prospectively,
opens to the engineered control of the selectivity of ORR pathways. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
energy transfer, hydroperoxyl, oxygen reduction reaction, SFG, single-atom catalysts, solvation
in
ACS Catalysis
volume
12
issue
13
pages
10 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85135043517
ISSN
2155-5435
DOI
10.1021/acscatal.2c02029
language
English
LU publication?
yes
id
be47dd44-2dc8-4426-bc33-e8537d00324b
date added to LUP
2022-11-29 12:51:47
date last changed
2022-11-30 13:29:50
@article{be47dd44-2dc8-4426-bc33-e8537d00324b,
  abstract     = {{The widely investigated oxygen reduction reaction (ORR) is well-known to<br>
 proceed via two competing routes, involving two or four electrons, and <br>
yielding different reaction products, respectively. Both pathways are <br>
believed to share a common, elusive intermediate, namely, the <br>
hydroperoxyl radical. By exploiting a cobalt single-atom biomimetic <br>
model catalyst, based on a self-assembled monolayer of Co-porphyrins <br>
grown on an almost free-standing graphene sheet, we identify, in situ at<br>
 room temperature in O<sub>2</sub>+H<sub>2</sub>O atmosphere, a hydroperoxyl-water cluster <br>
that is stabilized at the Co single-metal atom catalytic site. We show <br>
that the interplay between charge transfer, dipole and H-bonding, and <br>
water solvation behavior actually determines the hydroperoxyl-water <br>
complex stability, the Co-OOH bonding geometry, and, prospectively, <br>
opens to the engineered control of the selectivity of ORR pathways.}},
  author       = {{Armillotta, Francesco and Bidoggia, Davide and Baronio, Stefania and Biasin, Pietro and Annese, Antonio and Scardamaglia, Mattia and Zhu, Suyun and Bozzini, Benedetto and Modesti, Silvio and Peressi, Maria and Vesselli, Erik}},
  issn         = {{2155-5435}},
  keywords     = {{energy transfer; hydroperoxyl; oxygen reduction reaction; SFG; single-atom catalysts; solvation}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{13}},
  pages        = {{7950--7959}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Catalysis}},
  title        = {{Single Metal Atom Catalysts and ORR : H-Bonding, Solvation, and the Elusive Hydroperoxyl Intermediate}},
  url          = {{http://dx.doi.org/10.1021/acscatal.2c02029}},
  doi          = {{10.1021/acscatal.2c02029}},
  volume       = {{12}},
  year         = {{2022}},
}