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Title: Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad

Abstract

We report a self-assembled triad for artificial photosynthesis composed of a chromophore, carbon-dioxide reduction catalyst, and hydrogen oxidation complex, which is designed to operate without conventional sacrificial redox equivalents. Excitation of the zinc-porphyrin chromophore of the triad results in ultrafast charge transfer between a tungsten-alkylidyne donor and a rhenium diimine tricarbonyl acceptor, producing a charge-separated state that persists on the time scale of tens of nanoseconds and is thermodynamically capable of the primary dihydrogen and carbon dioxide binding steps for initiating the reverse water-gas shift reaction. The charge-transfer behavior of this system was probed using transient absorption spectroscopy in the visible, near-infrared, and mid-infrared spectral regions. Here, the behavior of the triad was compared with that of the zinc-porphyrin-rhenium-diimide dyad; the triad was found to have a significantly longer charge-separated lifetime than other previously reported porphyrin-rhenium diimine compounds.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Univ. of Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Chicago, IL (United States); Donaldson Co., Bloomington, MN (United States)
  3. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1606540
Grant/Contract Number:  
AC02-06CH11357; DGE-0638477; FG02-07-ER15910
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 123; Journal Issue: 51; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; redox reactions; absorption; catalysts; quenching; excited states

Citation Formats

La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., and Hopkins, Michael D.. Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcb.9b07830.
La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., & Hopkins, Michael D.. Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad. United States. https://doi.org/10.1021/acs.jpcb.9b07830
La Porte, Nathan T., Moravec, Davis B., Schaller, Richard D., and Hopkins, Michael D.. Fri . "Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad". United States. https://doi.org/10.1021/acs.jpcb.9b07830. https://www.osti.gov/servlets/purl/1606540.
@article{osti_1606540,
title = {Light-Driven Redox Activation of CO2- and H2-Activating Complexes in a Self-Assembled Triad},
author = {La Porte, Nathan T. and Moravec, Davis B. and Schaller, Richard D. and Hopkins, Michael D.},
abstractNote = {We report a self-assembled triad for artificial photosynthesis composed of a chromophore, carbon-dioxide reduction catalyst, and hydrogen oxidation complex, which is designed to operate without conventional sacrificial redox equivalents. Excitation of the zinc-porphyrin chromophore of the triad results in ultrafast charge transfer between a tungsten-alkylidyne donor and a rhenium diimine tricarbonyl acceptor, producing a charge-separated state that persists on the time scale of tens of nanoseconds and is thermodynamically capable of the primary dihydrogen and carbon dioxide binding steps for initiating the reverse water-gas shift reaction. The charge-transfer behavior of this system was probed using transient absorption spectroscopy in the visible, near-infrared, and mid-infrared spectral regions. Here, the behavior of the triad was compared with that of the zinc-porphyrin-rhenium-diimide dyad; the triad was found to have a significantly longer charge-separated lifetime than other previously reported porphyrin-rhenium diimine compounds.},
doi = {10.1021/acs.jpcb.9b07830},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 51,
volume = 123,
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
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