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

doi:10.1021/acs.jpca.8b00916

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

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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 similar to 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 mu s time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter similar to 300 ns time scale. In conclusion, this reaction scheme implies that we may withdraw two electrons from activated by a single photon.

Authors:

Huijser, Annemarie ^[1]; Pan, Qing ^[2]; van Duinen, David ^[3]; Laursen, Mads G. ^[4]; El Nahhas, Amal ^[5];

^[5];

^[6];

^[7];

^[8];

^[9]; Haldrup, Kristoffer ^[4];

^[10]; Smolentsev, Grigory ^[11];

^[5]

Univ. of Twente, Enschede (The Netherlands)
Univ. of Twente, Enschede (The Netherlands); Radboud Univ., Nijmegen (The Netherlands)
Univ. of Twente, Enschede (The Netherlands); Max Planck Institute for Polymer Research, Mainz (Germany)
Technical Univ. of Denmark, Lyngby (Denmark)
Lund Univ., Lund (Sweden)
Univ. of Vienna, Vienna (Austria); ETH Zurich, Zurich (Switzerland)
Univ. of Vienna, Vienna (Austria)
Argonne National Lab. (ANL), Argonne, IL (United States); Synchrotron SOLEIL, Gif-sur-Yvette Cedex (France)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Groningen, Groningen (The Netherlands)
Paul Scherrer Inst. (PSI), Villigen (Switzerland); Southern Federal Univ. of Russia, Rostov-on-Don (Russian Federation)

Publication Date:: Fri Jul 27 00:00:00 EDT 2018

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: Netherlands Organisation for Scientific Research (NWO); Knut and Alice Wallenberg Foundation; Ministry of Education and Science of the Russian Federation; USDOE

OSTI Identifier:: 1474854

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 122; Journal Issue: 31; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    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, and Uhlig, Jens. Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpca.8b00916.

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                    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.  United States.  https://doi.org/10.1021/acs.jpca.8b00916

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                    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, and Uhlig, Jens. Fri .  
"Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy".  United States.  https://doi.org/10.1021/acs.jpca.8b00916.  https://www.osti.gov/servlets/purl/1474854.

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@article{osti_1474854,

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

  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},

  abstractNote = {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 similar to 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 mu s time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter similar to 300 ns time scale. In conclusion, this reaction scheme implies that we may withdraw two electrons from activated by a single photon.},

  doi          = {10.1021/acs.jpca.8b00916},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 31,

  volume       = 122,

  place        = {United States},

  year         = {Fri Jul 27 00:00:00 EDT 2018},

  month        = {Fri Jul 27 00:00:00 EDT 2018}

}

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