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

Annemarie Huijser, Qing Pan, David Van Duinen, Mads G. Laursen, Amal El Nahhas, Pavel Chabera, Leon Freitag, Leticia González, Qingyu Kong, Xiaoyi Zhang, Kristoffer Haldrup, Wesley R. Browne, Grigory Smolentsev, Jens Uhlig (Corresponding Author)

Research output: Contribution to journalArticleAcademicpeer-review

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 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.

Original languageEnglish
Pages (from-to)6396-6406
Number of pages11
JournalJournal of physical chemistry A
Volume122
Issue number31
DOIs
Publication statusPublished - 9 Aug 2018

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X ray absorption spectroscopy
Photocatalysts
Hydrogen
Photoluminescence
Photons
Spectroscopy
X rays
Catalysts
Electrons
hydrogen
spectroscopy
absorption spectroscopy
x rays
photoluminescence
catalysts
photons
electronics
electrons

Keywords

  • UT-Hybrid-D

Cite this

Huijser, Annemarie ; Pan, Qing ; Van Duinen, David ; Laursen, Mads G. ; El Nahhas, Amal ; Chabera, Pavel ; Freitag, Leon ; González, Leticia ; Kong, Qingyu ; Zhang, Xiaoyi ; Haldrup, Kristoffer ; Browne, Wesley R. ; Smolentsev, Grigory ; Uhlig, Jens. / Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy. In: Journal of physical chemistry A. 2018 ; Vol. 122, No. 31. pp. 6396-6406.
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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 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.",
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Huijser, A, Pan, Q, Van Duinen, D, Laursen, MG, El Nahhas, A, Chabera, P, Freitag, L, González, L, Kong, Q, Zhang, X, Haldrup, K, Browne, WR, Smolentsev, G & Uhlig, J 2018, 'Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy' Journal of physical chemistry A, vol. 122, no. 31, pp. 6396-6406. https://doi.org/10.1021/acs.jpca.8b00916

Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy. / Huijser, Annemarie; Pan, Qing; Van Duinen, David; Laursen, Mads G.; El Nahhas, Amal; Chabera, Pavel; Freitag, Leon; González, Leticia; Kong, Qingyu; Zhang, Xiaoyi; Haldrup, Kristoffer; Browne, Wesley R.; Smolentsev, Grigory; Uhlig, Jens (Corresponding Author).

In: Journal of physical chemistry A, Vol. 122, No. 31, 09.08.2018, p. 6396-6406.

Research output: Contribution to journalArticleAcademicpeer-review

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AU - Huijser, Annemarie

AU - Pan, Qing

AU - Van Duinen, David

AU - Laursen, Mads G.

AU - El Nahhas, Amal

AU - Chabera, Pavel

AU - Freitag, Leon

AU - González, Leticia

AU - Kong, Qingyu

AU - Zhang, Xiaoyi

AU - Haldrup, Kristoffer

AU - Browne, Wesley R.

AU - Smolentsev, Grigory

AU - Uhlig, Jens

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N2 - 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.

AB - 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.

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JF - Journal of physical chemistry A

SN - 1089-5639

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