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Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy

Huijser, Annemarie LU ; Pan, Qing ; Van Duinen, David ; Laursen, Mads G. ; El Nahhas, Amal LU ; Chabera, Pavel LU ; Freitag, Leon ; González, Leticia ; Kong, Qingyu and Zhang, Xiaoyi , et al. (2018) In Journal of Physical Chemistry A 122(31). p.6396-6406
Abstract
Photoinduced electronic and structural changes of a hydrogen-generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and -chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (<30 ps) photoreduction of the Pt catalytic site, followed by an ∼600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex... (More)
Photoinduced electronic and structural changes of a hydrogen-generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and -chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (<30 ps) photoreduction of the Pt catalytic site, followed by an ∼600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex on a >10 μs time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter ∼300 ns time scale. This reaction scheme implies that we may withdraw two electrons from a catalyst that is activated by a single photon. (Less)
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published
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in
Journal of Physical Chemistry A
volume
122
issue
31
pages
6396 - 6406
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:30052048
  • scopus:85052053645
ISSN
1089-5639
DOI
10.1021/acs.jpca.8b00916
language
English
LU publication?
yes
id
3db7c66b-a34f-466d-9996-a94e9eb2786f
date added to LUP
2018-08-01 14:17:13
date last changed
2020-01-13 00:51:30
@article{3db7c66b-a34f-466d-9996-a94e9eb2786f,
  abstract     = {Photoinduced electronic and structural changes of a hydrogen-generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and -chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (&lt;30 ps) photoreduction of the Pt catalytic site, followed by an ∼600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex on a &gt;10 μs time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter ∼300 ns time scale. This reaction scheme implies that we may withdraw two electrons from a catalyst that is activated by a single photon.},
  author       = {Huijser, Annemarie and Pan, Qing and Van Duinen, David and Laursen, Mads G. and El Nahhas, Amal and Chabera, Pavel and Freitag, Leon and González, Leticia and Kong, Qingyu and Zhang, Xiaoyi and Haldrup, Kristoffer and Browne, Wesley R. and Smolentsev, Grigory and Uhlig, Jens},
  issn         = {1089-5639},
  language     = {eng},
  month        = {07},
  number       = {31},
  pages        = {6396--6406},
  publisher    = {The American Chemical Society (ACS)},
  series       = {Journal of Physical Chemistry A},
  title        = {Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy},
  url          = {http://dx.doi.org/10.1021/acs.jpca.8b00916},
  doi          = {10.1021/acs.jpca.8b00916},
  volume       = {122},
  year         = {2018},
}