Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution

Yang, Sizhuo; Fan, Donghua; Hu, Wenhui; Pattengale, Brian; Liu, Cunming; Zhang, Xiaoyi; Huang, Jier

doi:10.1021/acs.jpcc.8b00471

Title: Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H₂ Evolution

Abstract

Metal organic frameworks (MOFs) have emerged as novel scaffolds for artificial photosynthesis due to their unique capability in incorporating homogeneous photosensitizer and catalyst to their robust heterogeneous matrix. Here, we report the charge separation dynamics between molecular Ru-photosensitizer and Pt-catalyst, both of which were successfully incorporated into a Zr-MOF that demonstrates excellent activity and stability for light-driven H₂ generation from water. Using optical transient absorption (OTA) spectroscopy, we show that charge separation in this hybrid MOF occurs via electron transfer (ET) from Ru-photosensitizer to Pt-catalyst. Using Pt L₃-edge X-ray transient absorption (XTA) spectroscopy, we observed the intermediate reduced Pt site, directly confirming the formation of charge separated state due to ET from Ru-photosensitizer and unraveling their key roles in photocatalysis.

Authors:

Yang, Sizhuo ^[1]; Fan, Donghua ^[2]; Hu, Wenhui ^[1]; Pattengale, Brian ^[1]; Liu, Cunming ^[3];

^[3];

^[1]

Marquette Univ., Milwaukee, WI (United States). Dept. of Chemistry
Wuyi Univ., Jiangmen (China). School of Applied Physics and Materials
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division

Publication Date:: 2018-01-30

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); American Chemical Society Petroleum Research Fund (ACS PRF)

OSTI Identifier:: 1461304

Grant/Contract Number:: AC02-06CH11357; DMR-1654140; 57503-DNI6

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 6; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Yang, Sizhuo, Fan, Donghua, Hu, Wenhui, Pattengale, Brian, Liu, Cunming, Zhang, Xiaoyi, and Huang, Jier. Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution.  United States: N. p., 2018. 
Web.  https://doi.org/10.1021/acs.jpcc.8b00471.

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                    Yang, Sizhuo, Fan, Donghua, Hu, Wenhui, Pattengale, Brian, Liu, Cunming, Zhang, Xiaoyi, & Huang, Jier. Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution.  United States.  https://doi.org/10.1021/acs.jpcc.8b00471

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                    Yang, Sizhuo, Fan, Donghua, Hu, Wenhui, Pattengale, Brian, Liu, Cunming, Zhang, Xiaoyi, and Huang, Jier. Tue .  
"Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution".  United States.  https://doi.org/10.1021/acs.jpcc.8b00471.  https://www.osti.gov/servlets/purl/1461304.

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@article{osti_1461304,

  title        = {Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution},

  author       = {Yang, Sizhuo and Fan, Donghua and Hu, Wenhui and Pattengale, Brian and Liu, Cunming and Zhang, Xiaoyi and Huang, Jier},

  abstractNote = {Metal organic frameworks (MOFs) have emerged as novel scaffolds for artificial photosynthesis due to their unique capability in incorporating homogeneous photosensitizer and catalyst to their robust heterogeneous matrix. Here, we report the charge separation dynamics between molecular Ru-photosensitizer and Pt-catalyst, both of which were successfully incorporated into a Zr-MOF that demonstrates excellent activity and stability for light-driven H2 generation from water. Using optical transient absorption (OTA) spectroscopy, we show that charge separation in this hybrid MOF occurs via electron transfer (ET) from Ru-photosensitizer to Pt-catalyst. Using Pt L3-edge X-ray transient absorption (XTA) spectroscopy, we observed the intermediate reduced Pt site, directly confirming the formation of charge separated state due to ET from Ru-photosensitizer and unraveling their key roles in photocatalysis.},

  doi          = {10.1021/acs.jpcc.8b00471},

  journal      = {Journal of Physical Chemistry. C},

  number       = 6,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {1}

}

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https://doi.org/10.1021/acs.jpcc.8b00471

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Cited by: 4 works

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Figures / Tables:

Figure 1: Synthetic scheme (a) and SEM image of Ru-Pt-UIO-67 MOF. XRD patterns (c) and reflectance UV-visible spectra (d) of Ru-Pt-UIO-67, Pt-UIO-67, Ru-UIO-67 and UIO-67. (e) XANES spectra of Ru-Pt-UIO-67, Pt(dcbpy)Cl2 and Pt foil at Pt L3-edge. The inset shows their EXAFS spectra.

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Works referencing / citing this record:

Pristine Transition‐Metal‐Based Metal‐Organic Frameworks for Electrocatalysis
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DOI: 10.1039/c9ta09896h

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Journal of Physics: Condensed Matter, Vol. 31, Issue 48
DOI: 10.1088/1361-648x/ab38da

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Title: Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H2 Evolution

Abstract

Citation Formats

Figures / Tables:

Pristine Transition‐Metal‐Based Metal‐Organic Frameworks for Electrocatalysis journal, January 2019

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Title: Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H₂ Evolution

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journal, January 2019

On the potential for nanoscale metal–organic frameworks for energy applications
journal, January 2019

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journal, August 2019